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.

Alkenones in surface waters of the Nordic seas

Samples of filtered particulate organic matter (POM) were obtained during the summers of 1999 and 2000 from the surface waters of the Nordic seas to monitor the spatial distribution of long-chain alkenones. The aim of the study was to appraise existing alkenone-based climatic proxies in northern high latitudes. Unusually high percentages of the tetraunsaturated alkenone were measured in the polar waters of the East Greenland Current, with C37:4 of up to 77% in 80% of sea-ice cover. Values of percent C37:4 across the Nordic seas showed a strong association with water mass type. Analysis of coccoliths in filters indicated that calcified Emiliania huxleyi could not be discounted as the biological precursor of alkenones in all the water masses. A combined data set of 69 samples of POM revealed a stronger correlation of percent C37:4 to sea surface salinity (SSS; R2 = 0.72) than to sea surface temperature (SST; R2 = 0.50). Values of percent C37:4 in sea surface POM were much higher than those in surficial sediments of the northern North Atlantic. To explain the discrepancy in sedimentary and surface water column percent C37:4, we propose that the alkenone contents in surface sediments underlying arctic and polar waters are a combination of autochthonous and allochthonous inputs of alkenones. Our results show that percent C37:4 can be used to reconstruct the relative extension of arctic/polar water masses in the North Atlantic. However, the results prevent confirmation of percent C37:4 as a paleo-SSS proxy in the Nordic seas, given its multivariate nature in our data set and the decoupling between its range of values in surface waters and sediments.

Glacial-interglacial bioproductivity of the Mexican Margin

Sedimentary accumulation of biogenic components (organic carbon, opal, and biogenic barium) on the northwestern Mexican margin declined during every glacial interval of the past 140 kyr, indicating decreases in upwelling-induced productivity during cold periods. The glacial-interglacial contrasts in upwelling on this margin are attributed to reversals in land-ocean thermal contrast, the waxing and waning of the Laurentide Ice Sheet, and consequent responses of the western hemisphere wind fields. This scenario is consistent with three independent lines of evidence: terrestrial paleoclimatic data, general circulation model results, and our marine records. This pattern of glacial-interglacial variability in upwelling off NW Mexico is opposite to that observed in other low-latitude and midlatitude upwelling areas, such as the eastern equatorial Pacific. These results add to a growing pool of observations that the response of oceanic upwelling to glacial climatic forcing has been regionally variable.

Organic carbon content, stable isotopes and planktonic foraminifera in sediments of tghe norther Arabian Sea oxygen minimum zone

The northern Arabian Sea is one of the few regions in the open ocean where thermocline water is severely depleted in oxygen. The intensity of this oxygen minimum zone (OMZ) has been reconstructed over the past 225,000 years using proxies for surface water productivity, water column denitrification, winter mixing, and the aragonite compensation depth (ACD). Changes in OMZ intensity occurred on orbital and suborbital timescales. Lowest O2 levels correlate with productivity maxima and shallow winter mixing. Precession-related productivity maxima lag early summer insolation maxima by ~6 kyr, which we attribute to a prolonged summer monsoon season related to higher insolation at the end of the summer. Periods with a weakened or even non-existent OMZ are characterized by low productivity conditions and deep winter mixing attributed to strong and cold winter monsoonal winds. The timing of deep winter mixing events corresponds with that of periods of climatic cooling in the North Atlantic region.

(Table 1) Typical trace-fossil occurrences in DSDP Holes 56-436 and 56-435A

Trace fossils are in places abundant in cores from DSDP Leg 56 sites. They are particularly rich in the pelagic-clay sequence at Site 436. Some significant trace fossils, including Zoophycos, Teichichnus, Chondrites, rind and solid burrows, and pellet-armored rods, are described. The ichnofauna, except for pellet-armored rods in diatomaceous mudstone of the landward trench slope, is characterized by cosmopolitan bathyal to abyssal forms.

(Table A1) Chemical composition of abyssal peridotites from ODP Hole 153-920

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO2): at high fO2's, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO2 at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO2. V-MgO and V-Al2O3 systematics were found to be sensitive to fO2 variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO2 differences greater than ~2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al2O3 systematics that can be modeled by 1.5 GPa melting between FMQ - 3 and FMQ - 1. This is consistent with fO2's of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe3+ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO2's as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO2's in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO2 during partial melting, whereas the activity of Fe3+ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively. Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ~FMQ - 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO2's. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO2 content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO2's significantly greater than that of modern oceanic mantle. Instead, the fO2's inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.