Amino acids from ODP Holes 117-722B and 177-724C

Sedimentary d15N records are valuable archives of ocean history but they are often modified during early diagenesis. Here we quantify the effect of early diagenetic enrichment on sedimentary N-isotope composition in order to obtain the pristine signal of reactive N assimilated in the euphotic zone. This is possible by using paired data of d15N and amino acid composition of sediment samples, which can be applied to estimate the degree of organic matter degradation. We determined d15N and amino acid composition in coeval sediments from Ocean Drilling Program (ODP) Hole 772 B in the central Arabian Sea and from Hole 724 C situated on the Oman Margin in the western Arabian Sea coastal upwelling area. The records span the last 130 kyr and include two glacial-interglacial cycles. These new data are used in conjunction with data available for surface sediments that cover a wide range of organic matter degradation states, and with other cores from the northern and eastern Arabian Sea to explore spatial variations in the isotopic signal. In order to reconstruct pristine N values we apply the relationship between organic matter degradation and 15N enrichment in surface sediments to correct the core records for early diagenetic enrichment. Reconstructed d15N values suggest a significant role of N2-fixation during glacial stages. An evaluation of two preservation indices based on amino acid composition (Reactivity Index, RI; Jennerjahn and Ittekkot, 1997; and the Degradation Index, DI; Dauwe et al., 1999) in both recent sediments and core samples suggests that the RI is more suitable than the DI in correcting Arabian Sea d15N records for early diagenetic enrichment.

Calculated sea surface temperatures of two sediment cores

The reconstruction of ocean history employs a large variety of methods with origins in the biological, chemical, and physical sciences, and uses modern statistical techniques for the interpretation of extensive and complex data sets. Various sediment properties deliver useful information for reconstructing environmental parameters. Those properties that have a close relationship to environmental parameters are called ''proxy variables'' (''proxies'' for short). Proxies are measurable descriptors for desired (but unobservable) variables. Surface water temperature is probably the most important parameter for describing the conditions of past oceans and is crucial for climate modelling. Proxies for temperature are: abundance of microfossils dwelling in surface waters, oxygen isotope composition of planktic foraminifers, the ratio of magnesium or strontium to calcium in calcareous shells or the ratio of certain organic molecules (e.g. alkenones produced by coccolithophorids). Surface water salinity, which is important in modelling of ocean circulation, is much more difficult to reconstruct. At present there is no established method for a direct determination of this parameter. Measurements associated with the paleochemistry of bottom waters to reconstruct bottom water age and flow are made on benthic foraminifers, ostracodes, and deep-sea corals. Important geochemical tracers are d13C and Cd/Ca ratios. When using benthic foraminifers, knowledge of the sediment depth habitat of species is crucial. Reconstructions of productivity patterns are of great interest because of important links to current patterns, mixing of water masses, wind, the global carbon cycle, and biogeography. Productivity is reflected in the flux of carbon into the sediment. There are a number of fluxes other than those of organic carbon that can be useful in assessing productivity fluctuations. Among others, carbonate and opal flux have been used, as well as particulate barite. Furthermore, microfossil assemblages contain clues to the intensity of production as some species occur preferentially in high-productivity regions while others avoid these. One marker for the fertility of sub-surface waters (that is, nutrient availability) is the carbon isotope ratio within that water (13C/12C, expressed as d13C). Carbon isotope ratios in today's ocean are negatively correlated with nitrate and phosphate contents. Another tracer of phosphate content in ocean waters is the Cd/Ca ratio. The correlation between this ratio and phosphate concentrations is quite well documented. A rather new development to obtain clues on ocean fertility (nitrate utilization) is the analysis of the 15N/14N ratio in organic matter. The fractionation dynamics are analogous to those of carbon isotopes. These various ratios are captured within the organisms growing within the tagged water. A number of reconstructions of the partial pressure of CO2 have been attempted using d13C differences between planktic and benthic foraminifers and d13C values of bulk organic material or individual organic components. To define the carbon system in sea water, two elements of the system have to be known in addition to temperature. These can be any combination of total CO2 , alkalinity, or pH. To reconstruct pH, the boron isotope composition of carbonates has been used. Ba patterns have been used to infer the distribution of alkalinity in past oceans. Information relating to atmospheric circulationand climate is transported to the ocean by wind or rivers, in the form of minerals or as plant andanimal remains. The most useful tracers in this respect are silt-sized particles and pollen.

Mineralogical, sedimentological and paleontological analyses of ODP Hole 127-797B upper Quarternary sediments

Nearly continuous cores of Quaternary fine-grained sediments with distinct dark-light colored cycles were recovered from Sites 794, 795, and 797 in the basinal parts of the Japan Sea during Leg 127. A comparison of gray value (darkness) profiles supplemented by visual inspection of core photographs between sites indicated that most of the dark and light layers were correlatable between sites, and that two of the dark layers lie close to adjacent marker ash layers. These observations indicate that deposition of dark and light layers resulted from basin-wide synchronous events. In order to understand the origin of these dark-light cycles, petrographical, mineralogical, compositional, and paleontological studies were carried out on closely spaced samples from the upper Quaternary sediments recovered from Site 797. Age model was constructed based on comparison between variation in diatom abundance and the standard oxygen isotope curve of Imbrie et al. (1984), the latter was interpolated between the five age controlled levels established at Site 797. The two curves show similar patterns which enabled us to "tune" the sediment ages to the oxygen isotope stages. We have to use variation in diatom abundance as a substitute for oxygen isotope curve since oxygen isotopic data are not available at the studied sites. Bottom water oxygenation conditions were estimated based on two criteria: (1) the degree of lamina preservation and (2) the ratio of Corg to Stot. The surface water productivity was deduced from the Corg and biogenic silica content. Results suggest that the bottom water oxygenation level and the surface water productivity varied significantly in response to the glacial-interglacial cycles. Glacio-eustatic sea-level changes and subsequent changes in water circulation in the Japan Sea appear to have been responsible for these variations and consequent changes in sediment composition throughout the Quaternary.

Methane discharge in sediments of the Dvurechenskii mud volcano

During the MARGASCH cruise M52/1 in 2001 with RV Meteor we sampled surface sediments from three stations in the crater of the Dvurechenskii mud volcano (DMV, located in the Sorokin Trough of the Black Sea) and one reference station situated 15 km to the northeast of the DMV. We analysed the pore water for sulphide, methane, alkalinity, sulphate, and chloride concentrations and determined the concentrations of particulate organic carbon, carbonate and sulphur in surface sediments. Rates of anaerobic oxidation of methane (AOM) were determined using a radiotracer (14CH4) incubation method. Numerical transport-reaction models were applied to derive the velocity of upward fluid flow through the quiescently dewatering DMV, to calculate rates of AOM in surface sediments, and to determine methane fluxes into the overlying water column. According to the model, AOM consumes 79% of the average methane flux from depth (8.9 x 10**+ 6 mol a**-1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9 x 10**+ 6 mol a**-1. If it is assumed that all submarine mud volcanoes (SMVs) in the Black Sea are at an activity level like the DMV, the resulting seepage represents less than 0.1% of the total methane flux into this anoxic marginal sea. The new data from the DMV and previously published studies indicate that an average SMV emits about 2.0 x 10**+ 6 mol a**-1 into the ocean via quiescent dewatering. The global flux of dissolved methane from SMVs into the ocean is estimated to fall into the order of 10**+10 mol a**-1. Additional methane fluxes arise during periods of active mud expulsion and gas bubbling occurring episodically at the DMV and other SMVs.

Sediment geochemistry, foraminiferal fauna parameter, census counts and Varimax PC-factor loadings and scores of foraminiferal assemblages of sediment core GeoB12615-4

Analogous to West- and North Africa, East Africa experienced more humid conditions between approximately 12 to 5 kyr BP, relative to today. While timing and extension of wet phases in the North and West are well constrained, this is not the case for the East African Humid Period. Here we present a record of benthic foraminiferal assemblages and sediment elemental compositions of a sediment core from the East African continental slope, in order to provide insight into the regional shallow Indian Ocean paleoceanography and East African climate history of the last 40 kyr. During glacial times, the dominance of a benthic foraminiferal assemblage characterized by Bulimina aculeata, suggests enhanced surface productivity and sustained flux of organic carbon to the sea floor. During Heinrich Stadial 1 (H1), the Nuttallides rugosus Assemblage indicates oligotrophic bottom water conditions and therefore implies a stronger flow of southern-sourced AAIW to the study site. During the East African Humid Period, the Saidovina karreriana Assemblage in combination with sedimentary C/N and Fe/Ca ratios suggest higher river runoff to the Indian Ocean, and hence more humid conditions in East Africa. Between 8.5 and 8.1 kyr, contemporaneous to the globally documented 8.2 kyr Event, a severe reduction in river deposits implies more arid conditions on the continent. Comparison of our marine data with terrestrial studies suggests that additional moisture from the Atlantic Ocean, delivered by an eastward migration of the Congo Air Boundary during that time period, could have contributed to East African rainfall. Since approximately 9 kyr, the gaining influence of the Millettiana millettii Assemblage indicates a redevelopment of the East African fringe reefs.

Stable carbon and oxygen isotope record of Neogloboquadrina pachyderma and Cibicides lobatulus from the southwestern Greenland Sea

A core transect across the southwestern Greenland Sea reveals coeval events of extremely negative planktic and benthic delta13C excursions between 40 and 87 ka. The most pronounced event, event 1, began at peak Dansgaard-Oeschger stadial 22 (85 ka) with a duration of 18 k.y. During this episode, incursions of Atlantic Intermediate Water caused a bottom-water warming of up to 8 °C. The amplitude, timing, and geographic pattern of the delta13C events suggest that this bottom-water warming triggered clathrate instability along the East Greenland slope and a methane-induced depletion of delta13CDIC (DIC- dissolved inorganic carbon). Since delta13C event 1 matches a major peak in atmospheric CH4 concentration, this clathrate destabilization may have contributed to the rise in atmospheric CH4 and thus to climate warming over marine isotope stage 5.1.

Physical oceanography and hydrochemistry from the Laptev Sea, Arctic Ocean

Combined d18O/salinity data reveal a distinctive water mass generated during winter sea ice formation which is found predominantly in the coastal polynya region of the southern Laptev Sea. Export of the brine-enriched bottom water shows interannual variability in correlation with atmospheric conditions. Summer anticyclonic circulation is favoring an offshore transport of river water at the surface as well as a pronounced signal of brine-enriched waters at about 50 m water depth at the shelf break. Summer cyclonic atmospheric circulation favors onshore or an eastward, alongshore water transport, and at the shelf break the river water fraction is reduced and the pronounced brine signal is missing, while on the middle Laptev Sea shelf, brine-enriched waters are found in high proportions. Residence times of bottom and subsurface waters on the shelf may thereby vary considerably: an export of shelf waters to the Arctic Ocean halocline might be shut down or strongly reduced during "onshore" cyclonic atmospheric circulation, while with "offshore" anticyclonic atmospheric circulation, brine waters are exported and residence times may be as short as 1 year only.

Benthic foraminifera of the central Indian Ocean

Late Oligocene to late Pliocene vertical water-mass stratification along depth traverses in the northern Indian Ocean is depicted in this paper by benthic foraminifer index faunas. During most of this time, benthic faunas indicate well-oxygenated, bottom-water conditions at all depths except under the southern Indian upwelling and in the Pliocene in the southern Arabian Sea. Faunas suggest the initiation of lower oxygen conditions at intermediate depths in the northern Indian Ocean beginning in Oligocene Zone P21a. Lower oxygen conditions intensified during primary productivity pulses, possibly related to increased upwelling vigor, in the latest Oligocene and throughout most of the late middle through late Miocene. During times of elevated primary production, there may be more oxygen flux into sedimentary pore waters and the shallow infaunal habitat may become more oxygenated. One criterion for locating the source of "new" water masses is vertical homogeneity of benthic foraminifer indexes for well-oxygenated water masses from intermediate through abyssal depths. In the northern Mascarene Basin, this type of faunal homogeneity with depth corroborates the proposal that the northern Indian Ocean was an area of sinking well-oxygenated waters through most of the Miocene before Zone N17. Oxygenated, possibly "new" intermediate-water masses in the low- to middle-latitude Mascarene and Central Indian basins first developed in the late Oligocene. These well-oxygenated waters were probably more fertile than the Antarctic Intermediate Waters (AAIW) that cover intermediate depths in these areas today. Production of intermediate waters more similar to modern AAIW is indicated by the sparse benthic population of epifaunal rotaloid species in the northern Mascarene Basin during middle Miocene Zone N9 and from early through late Pliocene time. Deep-water characteristics are more difficult to interpret because of the extensive redeposition at the deeper sites. Redeposited intermediate, rather than shallow, water fossils and erosion from north to south in the Mascarene Basin are incompatible with the sluggish circulation from south to north through the western Indian Ocean basins today. Such erosion could result from the vigorous sinking of an intermediate-depth water mass of northern origin. Before late Oligocene Zone P22, benthic faunas indicate a twofold subdivision of the troposphere, with the boundary between upper and lower well-oxygenated water masses located from 2500-3000 mbsl. No characteristic bottom-water fauna developed before the end of late Oligocene Zone P22. Deep and abyssal benthic indexes suggest the development of water masses similar to those of the present day in the latest Miocene. Faunas containing deep-water benthic indexes, including the uvigerinids, suggestive of a water mass similar to modern Indian Deep Water (IDW), appeared during the late Miocene in the northern Mascarene and Central Indian basins. In the early Pliocene, this deep-water fauna was found only in the Central Indian Basin, whereas a fauna typical of modern Antarctic Bottom Water (AABW) spread through deep waters at 2800 mbsl in the Mascarene Basin. By late Pliocene Zone N21, however, deep-water faunas similar to their modern analogs were developed in both the eastern and western basins. Abyssal faunas, studied only in the Mascarene Basin, show more or less similarity to those under modern AABW. Bottom-water faunas containing Nuttallides umbonifera or Epistominella exiguua were first differentiated at the end of Zone P22, then appeared episodically during the early Miocene. These AABW-type faunas reappeared and migrated updepth into deep waters during the glacial episodes at the end of the Miocene and at the beginning of the Pliocene. By late Pliocene Zone N21, however, a bottom-water fauna similar to that under eastern Indian Bottom Water (IBW) developed in the Mascarene Basin. Modern bottom-water characteristics of the Mascarene Basin must have developed after ZoneN21.

Late Cretaceous-Early Neogene oxygen and carbon isotope record of the Indian Ocean

Stable isotopic data of calcareous nannofossil, monogeneric and monospecific planktic and benthic foraminifera from five Indian Ocean DSDP sites (212, 217, 220, 237, and 253), leads to the following paleoclimatic and paleoceanographic conclusions: - The latest Cretaceous oxygen isotopic record implies a cooling (3-4°C) during the Maastrichtian. At the Cretaceous/Tertiary boundary only a minor warming (about 2°C) has been recorded. The parallel delta13C decrease of more than 1? indicates a significant decrease in productivity. - During the latest Paleocene a positive delta13C excursion was detected in Sites 217 and 237. This transient enrichment in delta13C may be due to productivity changes on continents and/or a change in the storage rate of organic matter in marginal basins or shelf areas. - The most striking feature in the oxygen isotopic record is noted at the Early/Middle Eocene transition. The shift towards more positive values (which were probably enhanced to a certain extent by a preceding diagenetic alteration) delineates a dramatic climatic deterioration at high and mid latitudes during the earlier Tertiary. - Near the Eocene/Oligocene boundary a cooling is evident within the latest Eocene interval. During the earliest Oligocene time a hiatus at Sites 217 and 253 partially obscures the climatic record. - Several climatic fluctuations have been noted during the Oligocene: a cooling at the base of Zone NP 23, a warming at the top of Zone NP 23 through NP 24, and a cooling during Zone NP 25. - The Miocene oxygen isotopic record is dominated by changes in surface and bottom water environments during Zone NN5. The decreasing and then increasing delta18O values, together with the subsequent steepening of the vertical delta18O gradient, point towards major climatic instabilities. These events coincide with the Mid-Miocene build-up of Antarctic ice-sheets. During the latest Miocene to the earliest Pliocene the delta18O record of planktic foraminifera indicates a significant warming of the Indian Ocean at mid-latitudes. - The delta13C record during the Oligocene and Miocene reveals several cycles (delta13C enrichments: NP 24, NN2, NN5, NN9, and base NN 11) which are most likely related to changes in storage rates of organic matter and biological productivity due to climatic changes and transgression/regression cycles. In addition, changes in the circulation patterns may also have influenced the carbon isotopic record.

Maastrichtian calcareous nannofossils of Kronsmoor-Section

The latest Campanian-earliest Maastrichtian interval is well known as a period of intense climate cooling. This cooling caused a distinctive bipolar biogeographic distribution of calcareous nannofossil assemblages: High latitude settings were dominated by newly evolving endemic taxa, former cosmopolitan species disappeared at the same time and equatorial communities experienced an invasion of cool water taxa. The impact of this cooling on northern mid-latitude assemblages is, however, less well known. In order to overcome this gap we studied the Kronsmoor section (northwest Germany). This section provides a continuous upper Campanian - lower Maastrichtian succession with moderately to well preserved nannofossils. Uppermost Campanian assemblages are dominated by Prediscosphaera cretacea; other common taxa include Prediscosphaera stoveri, Watznaueria barnesiae and Micula staurophora. The lower Maastrichtian is characterized by lower numbers of P. cretacea and frequent Kamptnerius magnificus, Arkhangelskiella cymbiformis and Cribrosphaerella ehrenbergii. These changes reflect, in part, the Campanian-Maastrichtian boundary cooling since some successful taxa (e.g. K. magnificus) are related to cool surface waters. Other shifts in the nannofossil communities were perhaps the result of a changing nutrient regime. Stronger latitudinal gradients may have increased wind velocities and thus the eolian input of ferruginous dust required by N-fixing bacteria. The enhanced high latitude deep-water formation probably changed the bottom-water environment in disfavor of denitrificating organisms. A decline of chemical weathering and fluviatile transport may have reduced the amount of bioavailable phosphate. These processes led to an increased nitrate and a decreased phosphate content shifting the nutrient regime from nitrate towards phosphate limitation.

Benthic oxygen isotopes, Zr/Al and grain size fractions over the Miocene-Pliocene boundary in the Gulf of Cadiz

During the latest Messinian, hemipelagic sediments exhibiting precession-induced climate variability were deposited. These are overlain by Pliocene sediments deposited at a much higher sedimentation rate, with much higher and more variable XRF-scanning Zr/Al ratios than the underlying sediment, and that show evidence of winnowing, particle sorting and increasing grain size, which we interpret to be related to the increasing flow of MOW. Pliocene sedimentary cyclicity is clearly visible in both the benthic d18O record and the Zr/Al data and is probably also precessionally controlled. On the basis of these results, we conclude that contouritic sedimentation, associated with weak Mediterranean-Atlantic exchange, began in the Gulf of Cadiz virtually at or shortly after the Miocene-Pliocene boundary, with two contouritic bigradational sandy-beds within the fourth precession cycle after the Miocene-Pliocene boundary.

Dinoflagellate cysts and pollen distribution of marine surface sediments off West Africa

An organic-walled dinoflagellate cyst analysis was carried out on 53 surface sediment samples from West Africa (17-6°N) to obtain insight in the relationship between their spatial distribution and hydrological conditions in the upper water column as well as marine productivity in the study area. Multivariate analysis of the dinoflagellate cyst relative abundances and environmental parameters of the water column shows that sea-surface temperature, salinity, marine productivity and bottom water oxygen are the factors that relate significantly to the distribution patterns of individual species in the region. The composition of cyst assemblages and dinoflagellate cyst concentrations allows the identification of four hydrographic regimes; 1) the northern regime between 17 and 14°N characterized by high productivity associated with seasonal coastal upwelling, 2) the southern regime between 12 and 6°N associated with high-nutrient waters influenced by river discharge 3) the intermediate regime between 14 and 12°N influenced mainly by seasonal coastal upwelling additionally associated with fluvial input of terrestrial nutrients and 4) the offshore regime characterized by low chlorophyll-a concentrations in upper waters and high bottom water oxygen concentrations. Our data show that cysts of Polykrikos kofoidii, Selenopemphix quanta, Dubridinium spp., Echinidinium species, cysts of Protoperidinium monospinum and Spiniferites pachydermus are the best proxies to reconstruct the boundary between the NE trade winds and the monsoon winds in the subtropical eastern Atlantic Ocean. The association of Bitectatodinium spongium, Lejeunecysta oliva, Quinquecuspis concreta, Selenopemphix nephroides, Trinovantedinium applanatum can be used to reconstruct past river outflow variations within this region.