Geochemistry of sediments from the Tyrrhenian Sea

At Holes 650A and 651 A, set respectively in the Marsili Basin and the Vavilov Basin, Pleistocene sediments (turbiditic inputs interbedded with essentially hemipelagic sediments) may show layers of mudrocks with moderate to strong induration. Except in the two samples from Hole 651 A, it seems that zeolite crystallization does not play a role in the induration phenomenon. This latter appears to result from in situ clay authigenesis. Secondary K-Fe beidellite or Fe-Mg beidellite form diagenetic growths and bridges between sedimented particles. Turbidites are rich in volcaniclastics (glass, pumices and other volcanogenic elements) but the induration phenomenon appears to be associated essentially with the occurrence of basaltic detritus. It is proposed that clay authigenesis results from low temperature alteration of basaltic fragments issued from Vavilov and probably Marsili seamounts in sediments isolated from seawater by overlying deposits.

Hydro-sedimentary parameters measurements within the proglacial area of the Bossons glacier (Mont-Blanc massif, France)

This dataset presents hydro-sedimentary data within the Bossons glacier proglacial area. Bossons glacier is rapidly retreating and its proglacial area is deglaciated for ~ 30 years. It is an intriguing location to study periglacial, proglacial and subglacial erosion processes which requires estimating Total Dissolved Solid (TDS) and Total Suspended Solid (TSS) concentrations, and discharge. Measurements were performed at three distinct locations within Bosson glacier watershed : Bossons downstream (BDS), Bossons upstream (BUS) and Crosette (CRO). The latter is located at the glacier termini whereas BDS and BUS stations are farther downstream from the glacier, at 1.5 and 1.15 km, respectively .

Age models for sediment cores in the eastern tropical Pacific

We present new high-resolution N isotope records from the Gulf of Tehuantepec and the Nicaragua Basin spanning the last 50-70 ka. The Tehuantepec site is situated within the core of the north subtropical denitrification zone while the Nicaragua site is at the southern boundary. The d15N record from Nicaragua shows an 'Antarctic' timing similar to denitrification changes observed off Peru-Chile but is radically different from the northern records. We attribute this to the leakage of isotopically heavy nitrate from the South Pacific oxygen minimum zone (OMZ) into the Nicaragua Basin. The Nicaragua record leads the other eastern tropical North Pacific (ETNP) records by about 1000 years because denitrification peaks in the eastern tropical South Pacific (ETSP) before denitrification starts to increase in the Northern Hemisphere OMZ, i.e., during warming episodes in Antarctica. We find that the influence of the heavy nitrate leakage from the ETSP is still noticeable, although attenuated, in the Gulf of Tehuantepec record, particularly at the end of the Heinrich events, and tends to alter the recording of millennial timescale denitrification changes in the ETNP. This implies (1) that sedimentary d15N records from the southern parts of the ETNP cannot be used straightforwardly as a proxy for local denitrification and (2) that denitrification history in the ETNP, like in the Arabian Sea, is synchronous with Greenland temperature changes. These observations reinforce the conclusion that on millennial timescales during the last ice age, denitrification in the ETNP is strongly influenced by climatic variations that originated in the high-latitude North Atlantic region, while commensurate changes in Southern Ocean hydrography more directly, and slightly earlier, affected oxygen concentrations in the ETSP. Furthermore, the d15N records imply ongoing physical communication across the equator in the shallow subsurface continuously over the last 50-70 ka.

Thallium isotope composition in pyrites

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Sedimentology and gas hydrates of IODP Expedition 311 samples

Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8 km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49 mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23 cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63 µm) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245 mbsf.

Age models for ODP Leg 172 sites

Ten ODP sites drilled in a depth transect (2164-4775 m water depth) during Leg 172 recovered high-deposition rate (>20 cm/kyr) sedimentary sections from sediment drifts in the western North Atlantic. For each site an age model covering the past 0.8-0.9 Ma has been developed. The time scales have a resolution of 10-20 kyr and are derived by tuning variations of estimated carbonate content to the orbital parameters precession and obliquity. Based on the similarity in the signature of proxy records and the spectral character of the time series, the sites are divided into two groups: precession cycles are better developed in carbonate records from a group of shallow sites (2164-2975 m water depth, Sites 1055-1058) while the deeper sites (2995-4775 m water depth, Sites 1060-1063) are characterized by higher spectral density in the obliquity band. The resulting time scales show excellent coherence with other dated carbonate and isotope records from low latitudes. Besides the typical Milankovitch cyclicity significant variance of the resulting carbonate time series is concentrated at millennial-scale changes with periods of about 12, 6, 4, 2.5, and 1.5 kyr. Comparisons of carbonate records from the Blake Bahama Outer Ridge and the Bermuda Rise reveal a remarkable similarity in the time and frequency domain indicating a basin-wide uniform sedimentation pattern during the last 0.9 Ma.

Sapropels in the Mediterranean Sea

Eastern Mediterranean sediments are characterized by cyclic deposition of organic-rich sediments known as sapropels. Enhanced primary productivity combined with bottom water oxygen depletion are thought to be the main drivers for sapropel deposition. We selected sapropel layers from a suite of ODP-Leg 160 cores, and applied a set of geochemical proxies to determine paleo-productivity variations, redox conditions of the water column during deposition, and provenance of detrital material. High sedimentary Ba/Al and Corg contents indicate enhanced primary production, whereas the sedimentary La/Lu ratio, points to an enhanced contribution from a North African riverine source, during sapropel formation. These features are especially pronounced on Sapropels S5 and S7, deposited during a particularly warm climatic interval. This indicates a more intense North African drainage/weathering and consequently run-off for those sapropels that have the most enhanced expression of productivity too. Correspondingly, the latter has also resulted in bottom water redox conditions that have been more severe during these sapropels than during others. Deepwater formation from Adriatic and Aegean areas, thought to be mainly controlled by sustained cooling of preconditioned surface waters, triggers the onset of bottomwater ventilation, thus sapropel duration. Our data, therefore, suggest that the intensity of sapropel formation is determined by the North African monsoonal system, whereas their duration is directed by northern borderlands climatic conditions.

Physical properties and bulk minerals from IODP Holes 308-U1322B, U1322D and U1324B

How the micro-scale fabric of clay-rich mudstone evolves during consolidation in early burial is critical to how they are interpreted in the deeper portions of sedimentary basins. Core samples from the Integrated Ocean Drilling Program Expedition 308, Ursa Basin, Gulf of Mexico, covering seafloor to 600 meters below sea floor (mbsf) are ideal for studying the micro-scale fabric of mudstones. Mudstones of consistent composition and grain size decrease in porosity from 80% at the seafloor to 37% at 600 mbsf. Argon-ion milling produces flat surfaces to image this pore evolution over a vertical effective stress range of 0.25 (71 mbsf) to 4.05 MPa (597 mbsf). With increasing burial, pores become elongated, mean pore size decreases, and there is preferential loss of the largest pores. There is a small increase in clay mineral preferred orientation as recorded by high resolution X-ray goniometry with burial.

Bitumen and n-alkanes in organic matter from sedimentary rocks sampled in DSDP Holes 47-397A and 47-398

A study of samples from DSDP Leg 47 shows that transformation of organic matter in deep sea sediments is completly analogous to evolution of organic matter in sedimentary sequences on continents and depends on the same factors. Crucial among these factors are: genesis of organic matter, nature of its diagenetic changes, and current stage of catagenesis.

Composition of Fe-Mn nodules from the radiolarian belt of the Pacific Ocean

Typomorphic features of the main morphogenetic types of Fe-Mn nodules from the radiolarian belt have been considered on materials from polygons in the Clarion-Clipperton ore province and in the Central Basin of the Pacific Ocean. By character of surfaces, features of internal structure, mineral and chemical compositions, behavior of trace elements at selective leaching three genetic types of nodules have been divided: predominantly sedimentary, diagenetic, and sedimentary diagenetic. Their formation results from mechanism of growth.

High-resolution paleomagnetic investigation in the Iceland Basin

Based on discrete samples, we report new high-resolution records of the ~185 kyr Iceland Basin (IB) geomagnetic excursion from Ocean Drilling Project (ODP) Site 1063 on the Bermuda Rise (sedimentation rate 32 cm/kyr) and from ODP Site 983 in the far North Atlantic (sedimentation rate 18 cm/kyr). Two records from Holes 1063A and 1063B are very consistent, and provide the highest resolution of the detailed field behaviour during the IB excursion obtained so far. Inclination records from Holes 983B and 983C in the far North Atlantic are also very consistent, whereas declination anomalies deviate more notably. The pseudo-Thellier (PT) technique was applied along with more conventional palaeointensity proxies (NRM/ARM and NRM/kappa) to recover relative palaeointensity (RPI) estimates from Hole 1063A and Hole 983B. As expected, these proxies indicate that the field intensity generally dropped at both sites during the IB excursion, but also that the history of RPI from the two sites is different. VGPs from Site 1063 indicate that the field at this location experienced some stop-and-go behaviour between patches of intense vertical flux over North America and the tip of South America, areas which coincide fairly well with patches of preferred transitional VGP clustering from reversals and zones of high seismic velocity in the lower mantle. Changes in RPI at this location were generally gradual, possibly due to the proximity of these flux patches, and the first period of VGP-clustering over North America was accompanied by a conspicuous increase in RPI. VGPs from Site 983 track along a different path, and the associated RPI changes are very abrupt and completely synchronous with the onset and termination of the excursion. The differing VGP paths from Sites 1063 and 983 indicate that the global field structure during the IB excursion was not dominated by a single dipole.