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.

Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.

Past circulation along the western Iberian margin

Fifteen Iberian margin sediment cores, distributed between 43°12'N and 35°53'N, have been used to reconstruct spatial and temporal (sub)surface circulation along the Iberian margin since the Last Glacial period. Time-slice maps of planktonic foraminiferal derived summer sea surface temperature (SST) and export productivity (Pexp) were established for specific time intervals within the last 35 ky: the Holocene (Recent and last 8 ky), Younger Dryas (YD), Heinrich Stadials (HS) 1, 2a, 2b, 3, and the Last Glacial Maximum (LGM). The SST during the Holocene shows the same latitudinal gradient along the western Iberian margin as present-day with cold but productive areas that reflect the influence of coastal upwelling centers. The LGM appears as a slightly less warm, but more productive period relative to the Holocene and present-day conditions, suggesting that sea-level minima forced a westward displacement of the coastal upwelling centers possibly accompanied by a strengthening of northward winds. During the YD, a longitudinal thermal front is depicted at 10°W, with cold polar waters offshore and warmer subtropical waters inshore, suggesting that the subtropical Paleo-Iberian Poleward Current more likely flowed at a more inshore location masking the local SST signal and amplitude of variation. A substantial cooling and drop in productivity is observed during all HS, in particular HS1 and HS3, reflecting the penetration of icebergs-derived meltwater. These most extreme southward extensions of very cold waters define a strong SST gradient that marks a possible Paleo-Azores Front. Higher production south of this front was likely fed by frontal nutrient advection.

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.

Grain size and magnetic fabric analyses

The combined use of grain size and magnetic fabric analyses provides the ability to discriminate among depositional environments in deep-sea terrigenous sediments. We analyzed samples from three different depositional settings: turbidites, pelagic or hemipelagic interlayers, and sediment drifts. Results indicate that sediment samples from these different environments can be distinguished from each other on the basis of their median grain size, sorting, as well as the intensity and shape of magnetic fabric as determined from an examination of the anisotropy of magnetic susceptibility. We use these discriminators to interpret downcore samples from the Bermuda Rise sediment drift. We find that the finer grains of the Bermuda Rise (relative to the Blake Outer Ridge) do not result from lower depositional energy (current speed) and so may reflect a difference in the nature of sediment being delivered to the site (i.e., distance from source) between the two locations.

Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

Planktonic foraminifera stratigraphy of ODP Holes 198-1209C and 198-1211C

During Leg 198, the Cretaceous/Paleocene (K/P) boundary was recovered in a remarkable set of cores in nine separate holes at Sites 1209, 1210, 1211, and 1212 on the Southern High of Shatsky Rise. The boundary succession includes an uppermost Maastrichtian white to very pale orange, slightly indurated nannofossil ooze overlain by lowermost Paleocene grayish orange foraminiferal ooze. The boundary between the uppermost Maastrichtian and the lowermost Paleocene is clearly bioturbated. The contact surface is irregular, and pale orange burrows extend 10 cm into the white Maastrichtian ooze. Preliminary investigations conducted on board revealed that the deepest sections of these burrows yielded highly abundant, minute planktonic foraminiferal assemblages dominated by Guembelitria with rare Hedbergella holmdelensis and Hedbergella monmouthensis, possibly attributable to the lowermost Paleocene Zone P0. The substantial thickness of the uppermost Maastrichtian Micula prinsii (CC26) nannofossil Zone and the lowermost Danian Parvularugoglobigerina eugubina (Palpha) foraminiferal Zone suggested that the K/P boundary was rather expanded compared to the majority of deep-sea sites (see Bralower, Premoli Silva, Malone, et al., 2002, doi:10.2973/odp.proc.ir.198.2002). This data report concerns the planktonic foraminiferal biostratigraphy across the K/P boundary in Hole 1209C, the shallowest site (2387 m water depth), and in Hole 1211C, the deepest site (2907 m water depth), where the foraminiferal record across the boundary appeared to be best preserved.

Geochemical data and magnetic measurements of IODP Expedition 308, Hole U1319A from the Gulf of Mexico

A 160 m mostly turbiditic late Pleistocene sediment sequence (IODP Expedition 308, Hole U1319A) from the Brazos-Trinity intraslope basin system off Texas was investigated with paleo- and rock magnetic methods. Numerous layers depleted in iron oxides and enriched by the ferrimagnetic iron-sulfide mineral greigite (Fe3S4) were detected by diagnostic magnetic properties. From the distribution of these layers, their stratigraphic context and the present geochemical zonation, we develop two conceptual reaction models of greigite formation in non-steady depositional environments. The "sulfidization model" predicts single or twin greigite layers by incomplete transformation of iron monosulfides with polysulfides around the sulfate methane transition (SMT). The "oxidation model" explains greigite formation by partial oxidation of iron monosulfides near the iron redox boundary during periods of downward shifting oxidation fronts. The stratigraphic record provides evidence that both these greigite formation processes act here at typical depths of about 12-14 mbsf and 3-4 mbsf. Numerous "fossil" greigite layers most likely preserved by rapid upward shifts of the redox zonation denote past SMT and sea floor positions characterized by stagnant hemipelagic sedimentation conditions. Six diagenetic stages from a pristine magnetite-dominated to a fully greigite-dominated magnetic mineralogy were differentiated by combination of various hysteresis and remanence parameters.

Clay mineralogy on five NBP cores

During 2006, the SHALDRIL program recovered cores of Eocene through Pliocene material at four locations in the northwestern Weddell Sea, each representing a key period in the evolution of the Antarctic Peninsula ice cap. The recovered cores are not continuous, yet they provide a record of climate change with samples from the late Eocene, late Oligocene, middle Miocene, and early Pliocene and represent the only series of samples recovered from the northwestern Weddell Sea and spanning the Cenozoic and the initial growth of the peninsula ice cap. Late Eocene sediments sampled in the James Ross Basin are typically characterized by very dark greenish-gray muddy fine sand with some preserved burrowing and are interpreted to represent a shallow water continental shelf setting. Rare dropstones, primarily of well-cemented sandstones and minor ice-rafted material consisting of angular grains with glacially influenced surface features record the onset of mountain glaciation, the earliest such evidence in the region. The remaining cores were collected on the Joinville Plateau to the north of the James Ross Basin. The late Oligocene sediments consist of dark gray sandy mud with some clay lenses and many burrows, likely representing a distal delta or shelf setting. This core contains only very few and small dropstones, and the individual grains show decreased angularity and fewer glacial surface features relative to late Eocene deposits. The middle Miocene strata are composed of pebbly gray diamicton, representing proximal glacimarine sediments. The lower Pliocene section also contains many ice-rafted pebbles but is dominated by sandy units rather than diamicton and is interpreted to represent a current-winnowed deposit, similar to the modern contour current-influenced sediments of the region.

Geochemical analysis of surface sediments along the Portuguese Margin

Twenty-nine surface samples from the Portuguese shelf, recovered offshore from the mouths of the Ave, Douro, Lis and Mira rivers, were analysed using ICP-OES for selected major and trace elements, after total dissolution. Organic carbon, carbonate content and grain size were also determined. Five evaluation tools have been applied in order to compare the three study areas and to evaluate sediment geochemistry and other sediment compositional variability in the acquired samples: (1) empirical methods based on comparison with standard reference criteria, e.g. the NOAA sediment quality guidelines, (2) normalisation ratios using a grain-size proxy element, (3) "Gradient Method", plotting contaminant vs. organic matter or Al, (4) definition of a regional geochemical baseline from a compiled database, and (5) enrichment factors. The evaluation of element and component associations indicates differences related both to the onshore drainage areas and to the environmental shelf setting. Despite the considerable variability in total metal contents indicated by our results, the sediment metal composition is largely of natural origin. Metal enrichments observed in the Mira area are associated with the drainage of mineralised areas rich in Cu, Pb, Zn, Fe and Mn. The near absence of human impact on shelf sediments, despite the vicinity to urban areas with high industrialisation levels, such as the Ave-Douro and Lis areas, is attributed to effective trapping in the estuaries and coastal zones, as well dilution with less contaminated sediments shelf sediments and removal with fine fractions due to grain-size sorting. The character of the contaminated sediments transported to these shelf areas is further influenced by grain-size sorting as well as by dilution with less contaminated marine sediments. The results obtained individually by the different methods complement each other and allow more specific interpretations.

Foraminiferal assemblages of the Mackenzie-Beaufort Sea Slope and Amundsen Gulf

Two cores, one from the Beaufort Sea Slope at 1000 m water depth (core 750) and one from the Amundsen Gulf at 426 m (core 124), were collected to help determine paleo-ice cover in the Holocene and late glacial of this area. Site 750 is particularly sensitive to changes in paleo-ice cover because it rests beneath the present ice margin of the permanent Arctic ice pack. Core 124 was sampled just in front of the former glacier that moved out into the Amundsen Gulf and started to recede about 13 ka B.P. Both cores have a strong occurrence of calcareous foraminifera in the upper few centimeters, but these disappear throughout most of the Holocene, suggesting more open water in that time period than present. In the sediments representing the end of the last glacial period (dated at ~11,500-14,000 calibrated years B.P. (cal B.P.)) a calcareous fauna with an abundant planktic foraminiferal fauna suggests a return to almost permanent ice cover, much like the central Arctic today. Together with the foraminifera there was also abundant ice-rafted debris (IRD) in both cores between 12,000 cal B.P. and ~14,000 cal B.P., but those units are of different ages between cores, suggesting different events. The IRD in both cores appears to have the same magnetic and chemical signals, but their origins cannot be determined exactly until clay mineralogy is completed. There is abundant organic debris in both cores below the IRD units: the organics in core 750 are very diffuse and not visually identifiable, but the organic material in core 124 is clearly identifiable with terrestrial root fragments; these are 14C dated at over 37,000 years B.P. This is a marine unit as it also has glacial front foraminifera in the sediment with the organic debris that must have been originating from subglacial streams. The seismic and multibeam data both indicate glaciers did not cross the core 124 site.