Age determination of Antarctic marine sediments

We present the first circum-East Antarctic chronology for the Holocene, based on 17 radiocarbon dates generated by the accelerator method. Marine sediments from around East Antarctica contain a consistent, high-resolution record of terrigenous (ice-proximal) and biogenic (open-marine) sedimentation during Holocene time. This record demonstrates that biogenic sedimentation beneath the open-marine environment on the continental shelf has been restricted to approximately the past 4 ka, whereas a period of terrigenous sedimentation related to grounding line advance of ice tongues and ice shelves took place between 7 and 4 ka. An earlier period of open-marine (biogenic sedimentation) conditions following the late Pleistocene glacial maximum is recognized from the Prydz Bay (Ocean Drilling Program) record between 10.7 and 7.3 ka. Clearly, the response of outlet systems along the periphery of the East Antarctic ice sheet during the mid-Holocene was expansion. This may have been a direct consequence of climate warming during an Antarctic 'Hypsithermal'. Temperature-accumulation relations for the Antarctic indicate that warming will cause a significant increase in accumulation rather than in ablation. Models that predict a positive mass balance (growth) of the Antarctic ice sheet under global warming are supported by the mid-Holocene data presented herein.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Mineralogy ol late Quaternary marine sediments from the West and East Greenland shelves offshore from early Tertiary basalt outcrops

We use quantitative X-ray diffraction to determine the mineralogy of late Quaternary marine sediments from the West and East Greenland shelves offshore from early Tertiary basalt outcrops. Despite the similar basalt outcrop area (60 000-70 000 km**2), there are significant differences between East and West Greenland sediments in the fraction of minerals (e.g. pyroxene) sourced from the basalt outcrops. We demonstrate the differences in the mineralogy between East and West Greenland marine sediments on three scales: (1) modern day, (2) late Quaternary inputs and (3) detailed down-core variations in 10 cores from the two margins. On the East Greenland Shelf (EGS), late Quaternary samples have an average quartz weight per cent of 6.2 ± 2.3 versus 12.8 ± 3.9 from the West Greenland Shelf (WGS), and 12.02 ± 4.8 versus 1.9 ± 2.3 wt% for pyroxene. K-means clustering indicated only 9% of the samples did not fit a simple EGS vs. WGS dichotomy. Sediments from the EGS and WGS are also isotopically distinct, with the EGS having higher eNd (-18 to 4) than those from the WGS (eNd = -25 to -35). We attribute the striking dichotomy in sediment composition to fundamentally different long-term Quaternary styles of glaciation on the two basalt outcrops.

Geochemistry of recent marine sediments, interstitial water, and sea water from the West African continental margin

Carbon dioxide, ammonia, and reactive phosphate in the interstitial water of three sediment cores of the West African continental margin result from oxidation of sedimentary organic matter by bacterial sulfate reduction. The proposed model is a modification of one initially suggested by Richards (1965) for processes in anoxic waters: (CH2O)106 (NH3)8 (H3PO4) (0.7-0.2) + 53 SO4**2- =106 CO2 + 106 H20 + 8 NH3 + (0.7 - 0.2) H3PO4 + 53 S**2- The amount of reduced interstitial sulfate, the carbon-to-nitrogen-to-phosphorus atomic ratio of the sedimentary organic matter, as well as small amounts of carbon dioxide, which precipitated as interstitial calcium carbonate, are included in the general oxidation-reduction reaction. Preferential loss of nitrogen and phosphorus from organic matter close to the surface was recorded in both the interstitial water and sediment composition. It appeared that in deeper sections of the core organic carbon compounds were oxidized which were probably in an even lower oxidation state than that indicated by the proposed model. An estimated 2 % of the amount of organic matter still present was oxidized after it became incorporated into the sediment; whereas sulfide sulfur contents indicate that a much larger percentage (15-20%) seemed to have been subject to bacterial oxidation during the Pleistocene period, when a very thin oxidizing layer on the sediment allowed the above decomposition process to start relatively early favoured by almost fresh organic matter, and by almost unrestricted exchange of sulfate with the overlying water.

(Table 1) Sr, Nd and Os isotopic composition from marine sediments of the Bengal Fan

Sr, Nd, and Os isotopic data are presented for sediments from diverse locations in the Bay of Bengal. These data allow the samples to be divided into three groups, related to their sedimentary contexts. The first group, mainly composed of sediments from the shelf off Bangladesh and the currently active fan, has Sr and Nd characteristics consistent with a dominantly Himalayan source. Their 187Os/188Os ratios (~1.2-1.5) show that the average detrital material delivered by the Ganga-Brahmaputra (G-B) river system is not unusually radiogenic. A large difference in 187Os/188Os ratio exists between these Bengal Fan sediments and Ganga bedloads (187Os/188Os ~2.5, Pierson-Wickmann et al. (2000, doi:10.1016/S0012-821X(00)00003-0)). This difference mainly reflects addition of a less radiogenic Brahmaputra component, though mineralogical sorting and loss of radiogenic Os during transport may also play some role. The second sample group contains sediments from elsewhere in the Bay, particularly those located on the continental slope. They display Os isotopic compositions (0.99-1.11) similar to that of present seawater and higher Os and Re concentrations. These characteristics suggest the presence of a large hydrogenous contribution, consistent with the lower sedimentation rate of these samples. Sr and Nd ratios indicate that a significant fraction of these sediments is derived from erosion of non-Himalayan sources, such as the Indo-Burman range. These observations could be explained by the deflection of sediments from the G-B river system by westward currents in the head of the Bay. The third group contains only one sample, but shows that in addition to a Himalayan source, sediment discharge from Sri Lanka may influence the detrital component in the distal part of the fan. The similarity between the isotopic compositions of the group I R/V Sonne samples and those of Ocean Drilling Program Leg 116 (France-Lanord et al., 1993; Reisberg et al., 1997, doi:10.1016/S0012-821X(00)00003-0) suggests that the material eroding in the Himalayas has been roughly constant since the Miocene. The high Os isotopic ratios of leachates of both Sonne group I and Miocene Leg 116 sediments imply that much of the leachable highly radiogenic Os component was conserved during transport through the estuary or interaction with seawater. In constrast, samples with lower, but still relatively high, sedimentation rates (Sonne groups II and III and Pliocene Leg 116) seem to have significantly adsorbed or exchanged Os and Re with seawater. This suggests that in some cases the Os isotopic ratios of leachates of detrital sediments can be used to constrain the ancient marine Os record, or conversely, to date unfossiliferous sediments.

Strontium and neodymium concentrations and isotopic compositions of Arctic marine sediments

Sr and Nd isotopic compositions of Arctic marine sediments characterize changes of sediment source regions and trace shelf-ocean particle pathways during glacial-interglacial transitions in the eastern Arctic Ocean. In the 140-ka sedimentary record of a marine core from Yermak Plateau, north of Svalbard, 87Sr/86Sr ratios and epsion-Nd values vary between 0.717 and 0.740 and 39.3 and 314.9, respectively. Sr and Nd isotopic composition both change characteristically during glacial-interglacial cycles and are correlated with the extension of the Svalbard/Barents Sea ice sheet (SBIS). The downcore variation in Sr and Nd isotopic composition indicates climatically induced changes in sediment provenance from two isotopically distinct end-members: (1) Eurasian shelf sediments as a distal source; and (2) Svalbard bedrock as a proximal source that coincide with a change in transport mechanism from sea ice to glacial ice. During glacier advance from Svalbard and intensified glacial bedrock erosion, epsion-Nd values decrease gradually to a minimum value of 314.9 due to increased input of crystalline Svalbard bedrock material. During glacial maxima, the SBIS covered the entire Barents Sea shelf and supplied increasing amounts of Eurasian shelf material to the Arctic Ocean as ice rafted detritus (IRD). Epsion-Nd values in glacial sediments reach maximum values that are comparable to the average value of modern Eurasian shelf and sea ice sediments (epsion-Nd = 310.3). This confirms ice rafting as a major sediment transport mechanism for Eurasian shelf sediments into the Arctic Ocean and trace a sediment origin from the Kara Sea/Laptev Sea shelf area. After the decay of the shelf-based SBIS, the glacial shelf sediment spikes during glacial terminations I (epsion-Nd = 310.6) and II (epsion-Nd = 310.1) epsion-Nd values rapidly decrease to values of 312.5 typical for interglacial averages. The downcore Sr isotopic composition is anticorrelated to the Nd isotopic composition, but may be also influenced by grain-size effects. In contrast, the Nd isotopic composition in clay- to silt-size fractions of one bulk sediment sample is similar to within 0.3-0.8 epsion-Nd units and seems to be a grain-size independent provenance tracer.

Bulk sediment and diatom silica carbon isotope composition from Antarctic coastal marine sediments

Organic carbon occluded in diatom silica is assumed to be protected from degradation in the sediment. d13C from diatom carbon (d13C(diatom)) therefore potentially provides a signal of conditions during diatom growth. However, there have been few studies based on d13C(diatom). Numerous variables can influence d13C of organic matter in the marine environment (e.g., salinity, light, nutrient and CO2 availability). Here we compare d13C(diatom) and d13C(TOC) from three sediment records from individual marine inlets (Rauer Group, East Antarctica) to (i) investigate deviations between d13C(diatom) and d13C(TOC), to (ii) identify biological and environmental controls on d13C(diatom) and d13C(TOC), and to (iii) discuss d13C(diatom) as a proxy for environmental and climate reconstructions. The records show individual d13C(diatom) and d13C(TOC) characteristics, which indicates that d13C is not primarily controlled by regional climate or atmospheric CO2 concentration. Since the inlets vary in water depths offsets in d13C are probably related to differences in water column stratification and mixing, which influences redistribution of nutrients and carbon within each inlet. In our dataset changes in d13C(diatom) and d13C(TOC) could not unequivocally be ascribed to changes in diatom species composition, either because the variation in d13C(diatom) between the observed species is too small or because other environmental controls are more dominant. Records from the Southern Ocean show depleted d13C(diatom) values (1-4 per mil) during glacial times compared to the Holocene. Although climate variability throughout the Holocene is low compared to glacial/interglacial variability, we find variability in d13C(diatom), which is in the same order of magnitude. d13C of organic matter produced in the costal marine environment seems to be much more sensitive to environmental changes than open ocean sites and d13C is of strongly local nature.

C1-C8 hydrocarbons in marine sediments

Light hydrocarbon (C1-C8) profiles are compared for three wells of varying maturities: two immature DSDP wells (Site 397 near the Canary Islands and Site 530A near the Walvis Ridge in the south-east Atlantic) and a mature well, the East Cameron well in the Texas Gulf Coast. Primary migration of C1 and C2 appears to be occurring in all of the sedimentary rocks examined. Primary migration of C3+ components becomes important only as fine-grained sedimentary rocks enter the catagenetic hydrocarbon generation zone or over short distances in more permeable sections. Lateral migration along bedding planes was more important than vertical migration in sedimentary rocks of all maturities. The lightest (methane, ethane and propane gases) hydrocarbon show greater fractionation than do the C4-C8 alkanes which generally show minimal fractionation during the migrational process. Subsurface diffusion coefficients for these p.p.b. quantities of C2-C5 alkanes from immature sediments from DSDP Site 530 are estimated to be several orders of magnitude less than values reported in the literature for diffusion of much larger amounts of these compounds from mature water wet sediments into air or sandstones. Since our calculations suggest light hydrocarbons are present in amounts less than their reported solubilities in pure water at 25°C, we postulate that the sediment organic matter has a substantial effect on retarding the movement of these light hydrocarbons.

Germanium content in marine sediments

In the geosphere, germanium (Ge) has a chemical behavior close to that of silicon (Si), and Ge commonly substitutes for Si (in small proportions) in silicates. Studying the evolution of the respective proportions of Ge and Si through time allows us to better constrain the global Si cycle. The marine inventory of Ge present as dissolved germanic acid is facing two main sinks known through the study of present sediments: 1) incorporation into diatom frustules and transfer to sediments by these "shuttles", 2) capture of Ge released to pore water through frustule dissolution by authigenic mineral phases forming within reducing sediments. Our goals are to determine whether such a bio-induced transfer of Ge is also achieved by radiolarian and whether Ge could be trapped directly from seawater into authigenic phases with no intervention of opal-secreting organisms (shuttles). To this end, we studied two Paleozoic radiolarite formations and geological formations dated of Devonian, Jurassic and Cretaceous, deposited under more or less drastic redox conditions. Our results show that the Ge/Si values observed for these radiolarites are close to (slightly above) those measured from modern diatoms and sponges. In addition, our results confirm what is observed with some present-day reducing sediments: the ancient sediments that underwent reducing depositional conditions are authigenically enriched in Ge. Furthermore, it is probable that at least a part of the authigenic Ge came directly from seawater. The recurrence and extent (through time and space) of anoxic conditions affecting sea bottoms have been quite important through the geological times; consequently, the capture of Ge by reducing sediments must have impacted Ge distribution and in turn, the evolution of the seawater Ge/Si ratio.

Mg/Ca and Sr/Ca in calcites and estimated distribution coefficients in marine sediments (Table 2)

Recrystallization processes in marine sediments can alter the extent to which biogenic calcite composition serves as a proxy of oceanic chemical and isotopic history. Models of calcite recrystallization developed to date have resulted in significant insights into these processes, but are not completely adequate to describe the conditions of recrystallization. Marine sediments frequently have concentration gradients in interstitial dissolved calcium, magnesium, and strontium which have probably evolved during sediment accumulation. Realistic, albeit simplified, models of the temporal evolution of interstitial water profiles of Ca, Mg, and Sr were used with several patterns of recrystallization rate variation to predict the composition of recrystallized inorganic calcite. Comparison of predictions with measured Mg/Ca and Sr/Ca ratios in severely altered calcite samples from several Deep Sea Drilling Project sites demonstrates that models incorporating temporal variation in interstitial water composition more successfully predict observed calcite compositions than do models which rely solely on present-day interstitial water chemistry. Temporal changes in interstitial composition are particularly important in interpreting Mg/Ca ratios in conjunction with Sr/Ca ratios. Estimates of Mg distribution coefficients from previous observations in marine sediments, much lower than those in laboratory studies of inorganic calcite, are confirmed by these results. Evaluation of the effects of diagenetic alteration of biogenic calcium carbonate sediment must be a site-specific process, taking into account accumulation history, present interstitial chemistry and its variation in the past, and sample depths and ages.

n-Alkane analyses from an transect of marine surface sediments off southwest Africa

An isobathic transect of marine surface sediments from 1°N to 28°S off southwest Africa was used to further evaluate the potential of the chain length distribution and carbon stable isotope composition of higher plant n-alkanes as proxies for continental vegetation and climate conditions. We found a strong increase in the n-C29-33 weighted mean average d13C values from -33 per mil near the equator to around -26 per mil further south. Additionally, C25-35n-alkanes reveal a southward trend of increasing average chain length from 30.0 to 30.5. The data reflect the changing contribution of plants employing different photosynthetic pathways (C3 and C4) and/or being differently influenced by the environmental conditions of their habitat. The C4 plant proportions calculated from the data (ca. 20% for rivers draining the rainforest, to ca. 70% at higher latitude) correspond to the C4 plant abundance in continental catchment areas postulated by considering prevailing wind systems and river outflows. Furthermore, the C4 plant contribution to the sediments correlates with the mean annual precipitation and aridity at selected continental locations in the postulated catchment areas, suggesting that the C4 plant fraction in marine sediments can be used to assess these environmental parameters.