Geochemistry of pore water and sediments from Exmouth Plateau

During Leg 122, a transect was drilled across the Wombat Plateau, a marginal spur of the Exmouth Plateau, complemented by two sites on the Exmouth Plateau proper. In this report, pore-water analyses for major seawater constituents, alkalinity, Ba, Fe, Mn, Li, Sr, Rb, and silica are presented. Large gradients in the pore-water profiles provide evidence of complex sediment/pore-water interactions associated with carbonate and silica diagenesis and the formation of authigenic minerals. Diffusion affects pore-water profiles but differs considerably from site to site. Advection of freshwater, probably of continental origin, helps maintain negative Cl and salinity gradients deep within the sediments of the Exmouth Plateau.

Eocene-Oligocene calcareous nannofossil events of ODP Sites from the Southern Ocean

The evolution of the Southern Ocean climate during the late Eocene-late Oligocene interval is examined through highresolution, quantitative calcareous nannofossil analyses on samples from the Southern Ocean sections on Maud Rise and Kerguelen Plateau. We determined the abundance patterns of the counted species to clarify the biostratigraphy, which we correlated with high-resolution magnetostratigraphy [Roberts, A.P., Bicknell, S.J., Byatt, J., Bohaty, S.M., Florindo, F., Harwood, D.M., 2003a. Magnetostratigraphic calibration of Southern Ocean diatom datums from the Eocene-Oligocene of Kerguelen Plateau (Ocean Drilling Program Sites 744 and 748). In: Florindo, F., Cooper, A.K., O'Brien, P.A. (Eds.), Antarctic Cenozoic Palaeoenvironments: Geologic Record and Models. Palaeogeogr., Palaeoclimatol., Palaeoecol. 198 145-168; Florindo, F., Roberts, A.P., in press. Eocene-Oligocene magnetobiochronology of ODP Sites 689 and 690, Maud Rise, Weddell Sea, Antarctica. Geol. Soc. Am. Bull.], and used this data to interpret paleoceanographic changes through the late Eocene to late Oligocene. Percentage plots of the individual species, compared with R-mode principal component and cluster analysis results, allowed us to divide the assemblages into three groups: temperate-water taxa, cool-water taxa, and no temperature-affinity taxa. We attempt correlations between these paleoecological groups and the major sea-surface temperature (SST) variations with tectonic and paleoceanographic changes in the Southern Ocean. During the late Eocene, the nannofossil assemblage data reveal that there were several minor SST decreases (coolings) from 36 to 34 Ma, before the Eocene/Oligocene (E/O) boundary. A sharp cooling event, dated at 33.54 Ma (earliest Oligocene), occurred about 160 kyr after the E/O boundary, which is dated at 33.7 Ma. Relatively stable, cool conditions are interpreted to persist until the latest Oligocene, when an increase in abundance of temperate-water taxa, which corresponds to an antithetical decrease in abundance of cool-water indicators, is recorded. On the basis of our dating, the opening of the Drake Passage, allowing shallow-water circulation, began by 33.54 Ma at the latest, while the establishment of deep-water connections through the Tasmanian Gateway occurred at 33 Ma, as suggested by Exon et al. [Proc. ODP, Init. Rep. 189 (2001) 1].

Calcium carbonate, sedimentation and mass accumulation rates at DSDP Site 85-572

At Site 572, located at 1°N, 114° W (3903 m water depth), we recovered a continuous hydraulic piston cored section of upper Miocene to upper Pleistocene pelagic sediments. The sediment is composed of biogenic carbonate and silica with nonbiogenic material as a minor component. Detailed analysis of the calcium carbonate content shows that the degree of variability in carbonate deposition apparently changed markedly between the late Miocene and Pliocene at this equatorial Pacific site. During this interval carbonate mass accumulation rates decreased from 2.6 to 0.8 g/cm**2 per 10**3 yr. If we assume that variations in CaCO3 content reflect changes in the degree of dissolution, then the detailed carbonate analysis would suggest that the degree of variability in carbonate deposition decreases by a factor of 5 as the dominant wavelength of variations increases significantly. However, if the variability in carbonate concentration is described in terms of changes in mean mass accumulation, calculations then suggest that relatively small changes in noncarbonate rates may be important in controlling the observed carbonate records. In addition, the analysis suggests that the degree of variability observed in pelagic carbonate data may in part reflect total accumulation rates. Intervals with high sedimentation rates show lower amplitude variations in concentration than intervals with lower sedimentation rates for the same degree of change in the carbonate accumulation rate.

Geochemical investigation of ODP Leg 113 sites

Dissolved organic carbon (DOC) was determined in pore water extracted from pelagic and hemipelagic sediments recovered during Leg 113. DOC concentration varied between 1.82 and 13.6 mg C/L which is one to two orders of magnitude less than previously reported for hemipelagic sediments. It is argued that this difference is related to differences in the intensity of degradation of organic matter. As a first approximation it is found that in reducing sediments, the level of DOC is proportional to the intensity of sulfate reduction. It is suggested that DOC is formed by different mechanisms in oxic and reducing environments.

Nannofossil biostratigraphy of ODP Site 210-1276 sediments

Ocean Drilling Program (ODP) Leg 210 is one of very few deep-sea legs drilled along the eastern Canadian continental margin. Most other drilling on this margin has been carried out by the petroleum industry on the shallow-water regions of the Scotian shelf and the Grand Banks (see Doeven, 1983, for nannofossil studies). Deep Sea Drilling Project (DSDP) Leg 12 Site 111 and ODP Leg 105 Site 647 were drilled in the general vicinity of Leg 210 but recovered no appreciable Lower Cretaceous (Albian-Cenomanian) sediments. Site 111 yielded indurated limestones dated tentatively as late Albian-early Cenomanian, whereas Site 647 encountered no Albian-Cenomanian sediments. Two sites (Sites 1276 and 1277) were drilled during Leg 210 in the Newfoundland Basin with the primary objective of recovering basement rocks to elucidate the rifting history of the North Atlantic Basin. The location for Leg 210 was selected because it is conjugate to the Iberia margin, which was drilled extensively during DSDP/ODP Legs 47B, 103, 149, and 173. A secondary but equally important objective was to recover the overlying sediments with the purpose of studying the postrift sedimentation history of this margin.

Interstitial-water chemistry of ODP Leg 113 sites

Variations in the distribution of major elements and stable oxygen isotopes in ODP Leg 113 pore water are not related to lithology and thus appear to be controlled by minor constituents. Petrographic observations and geochemical considerations indicate that alteration of calc-alkalic volcanic material dispersed in the sediment is an important process. A diagenetic reaction is constructed that involves transformation of volcanic glass into smectite, zeolite (represented by phillipsite), chert, and iron sulfide. Mass balance calculations reveal that alteration of less than 10% (volume) of volcanogenic material may account for the observed depletion of magnesium, potassium, and 18O and enrichment of calcium. Alteration of this amount of volcanic glass produces less than 4% (volume) of smectite and zeolite. Hence, mass balance is obtained without having to invoke unreasonable large amounts of volcanic matter or interactions between seawater and basement.

Mineralogy and geochemistry of Miocene tuff from ODP Hole 129-802A

Drilling at Ocean Drilling Program Site 802 in the central Mariana Basin, northwest Pacific Ocean, revealed an unexpected 222-m-thick sequence of well-cemented tuff of Miocene age. The deposits are unusual in that their source is presumably an unmapped seamount and they exhibit several peculiar petrological and mineralogical features. The well-developed secondary mineral sequence which includes analcime is rare in such relatively young, unburied deposits, in an area where there is little other evidence of hydrothermal activity. The massive tuff section also contains abundant fissure veins made of a rare silicate carbonate sulfate hydroxide hydrate of calcium, called thaumasite, which has not before been described in deep submarine deposits. The smectite-zeolite-thaumasite paragenesis coincides with the presence of chloride and calcium-enriched interstitial waters. The diagenetic evolution of the deposit appears to have been largely controlled by the depositional mode. The discharges of disaggregated and rejuvenated volcaniclasts seem to have been abrupt and repeated. The Miocene tuff at Site 802 thus provides new insights on the interactions between basaltic glass, biogenic phases, and seawater, in a specific deep-sea environment.

Planktonic foraminifera oxygen isotope and trace metal data ODP Hole 172-1056A, 46-54 ka BP

Salinity increase in the subtropical gyre system may have pre-conditioned the North Atlantic Ocean for a rapid return to stronger overturning circulation and high-latitude warming following meltwater events during the Last Glacial period. Here we investigate the Gulf Stream - subtropical gyre system properties over Dansgaard-Oeschger (DO) cycles 14 to 12, including Heinrich ice-rafting event 5. During the Holocene and Last Glacial Maximum a positive gradient in surface dwelling planktonic foraminifera d18O (Globigerinoides ruber) can be observed between the Gulf Stream and subtropical gyre, due to decreasing temperature, increasing salinity, and a change from summer to year-round occurrence of G. ruber. We assess whether this gradient was a common feature during stadial-interstadial climate oscillations of Marine Isotope Stage 3, by comparing existing G. ruber d18O from ODP Site 1060 (subtropical gyre location) and new data from ODP Site 1056 (Gulf Stream location) between 54 and 46 ka. Our results suggest that this gradient was largely absent during the period studied. During the major warm DO interstadials 14 and 12 we infer a more zonal and wider Gulf Stream, influencing both ODP Sites 1056 and 1060. A Gulf Stream presence during these major interstadials is also suggested by the large vertical d18O gradient between shallow dwelling planktonic foraminifera species, especially G. ruber, and the deep dwelling species Globorotalia inflata at site 1056, which we associate with strong summer stratification and Gulf Stream presence. A major reduction in this vertical d18O gradient from 51 ka until the end of Heinrich event 5 at 48.5 ka suggests site 1056 was situated within the subtropical gyre in this mainly cold period, from which we infer a migration of the Gulf Stream to a position nearer to the continental shelf, indicative of a narrower Gulf Stream with possibly reduced transport.

Marine osmium isotope record across the Cretaceous-Tertiary boundary

A composite late Maastrichtian (65.5 to 68.5 Ma) marine osmium (Os) isotope record, based on samples from the Southern Ocean (ODP Site 690), the Tropical Pacific Ocean (DSDP Site 577), the South Atlantic (DSDP Site 525) and the paleo-Tethys Ocean demonstrates that subaerially exposed pelagic carbonates can record seawater Os isotope variations with a fidelity comparable to sediments recovered from the seafloor. New results provide robust evidence of a 20% decline in seawater 187Os/188Os over a period of about 200 kyr early in magnetochron C29r well below the Cretaceous-Paleogene Boundary (KPB), confirming previously reported low-resolution data from the South Atlantic Ocean. New results also confirm a second more rapid decline in 187Os/188Os associated with the KPB that is accompanied by a significant increase in Os concentrations. Complementary platinum (Pt) and iridium (Ir) concentration data indicate that the length scale of diagenetic remobilization of platinum group elements from the KPB is less than 1 m and does not obscure the pre-KPB decline in 187Os/188Os. Increases in bulk sediment Ir concentrations and decreases in bulk carbonate content that coincide with the Os isotope shift suggest that carbonate burial flux may have been lower during the initial decline in 187Os/188Os. We speculate that diminished carbonate burial rate may have been the result of ocean acidification caused by Deccan volcanism.