Minerals and geochemistry of DSDP Hole 81-552A

The acid insoluble coarse fractions of the glacial-interglacial sequence of Hole 552A in the NE Atlantic are made up of varying amounts of terrigenous detritus, biogenic silica, and pyroclastic material, principally volcanic glass. Volcanic ash content varies significantly over the entire interval, and the three North Atlantic ash horizons of Ruddiman and Glover (1972) can be recognized satisfactorily. The terrigenous detritus is of mixed metamorphic-basaltic type and probably originated on the Greenland landmass

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

Bulk and clay mineralogy of ODP Leg 110 holes

The mineralogy of both bulk- and clay-sized fractions of samples from Sites 671, 672, and 674 of ODP Leg 110 was determined by X-ray diffraction. The major minerals include quartz, calcite, plagioclase feldspar, and the clay minerals smectite, illite, and kaolinite. The smectite is a dioctahedral montmorillonite and is derived primarily from degradation of volcanic ash. Percentage of smectite varies with sediment age; Miocene and Eocene sediments are the most smectite-rich. High smectite content tends to correlate with elevated porosity, presumably because of the ability of smectite clays to absorb significant amounts of interlayer water. Because of a change in physical properties, the decollement zone at Site 671 formed in sediments immediately subjacent to a section of smectite-rich, high-porosity, Miocene-age sediments. Sediments above the decollement at Site 671, as well as all sediments analyzed from Sites 672 and 674, contain nearly pure smectite characteristic of the alteration of volcanic ash. Within the decollement zone and underthrust sequence, however, the smectite contains up to 65% illite interlayers. Although the illite/smectite could be interpreted as detrital clay derived from South America, its absence in the sediments stratigraphically equivalent to the decollement and underthrust sequences at Sites 672 and 674 favors the interpretation that it originated by diagenetic alteration of pre-existing smectite similar to that in the overlying sediments. A significant percentage of the freshening of the pore waters observed in these zones could be due to the water released during smectite dehydration.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Miocene radiolarians of the Sulu Sea

Radiolarians are sporadic in sediments collected in the Sulu Sea during ODP Leg 124. Due to the generally poor preservation and low abundance of radiolarians in Sulu Sea sediments, no biostratigraphic datums are well defined, although three radiolarian zones are identified. Most samples containing radiolarians are pelagic or hemipelagic clays with varying proportions of volcanic ash. Detailed analysis of Sulu Sea radiolarians was limited to Miocene successions. Pliocene and Quaternary occurrences of radiolarians were noted but have not been zoned. The late middle Miocene of Sites 769 and 771 is represented by an assemblage of radiolarians (Diartus petterssoni Zone) that is entirely replaced by massive pyrite. This type of preservation develops only under anoxic conditions. The development of widespread anoxia in Sulu Sea waters in the late middle Miocene was probably the result of hydrologic isolation of basin waters, and may be associated with eustatic sea level fall over the silled basin. Upper lower Miocene pelagic and hemipelagic sediments that overlie pyroclastics and basalt flows in the Sulu Sea sites contain moderately to very poorly preserved radiolarians of the Calocycletta costata Zone. A thin unit of marine claystone was recovered from between the thick pyroclastics and basement rocks at Site 768. Radiolarians present in these claystones are rare and very poorly preserved. This radiolarian assemblage probably represents the C. costata Zone, although very poor preservation and low abundance make this interpretation equivocal. The radiolarian zones identified constrain the age of basin formation to late early Miocene or earlier.

Geochemistry at DSDP Legs 56-57 Holes

About 200 volcanic ash layers were recovered during DSDP Leg 57. The volcanic glass in some of these layers was investigated petrographically and chemically in this study. Volcanic glass is mainly rhyolitic and/or rhyodacitic in chemical composition, and its refractive index ranges from 1.496 to 1.529. Some volcanic ash layers consist of multiple grains of different chemical compositions. All the volcanic glass belongs to the tholeiitic and the calc-alkalic volcanic rock series, in SiO2-(Na2O + K2O) diagram and FeO*/MgO-SiO2 diagram. We correlated successfully three volcanic ash layers from the standpoint of chemical composition and biostratigraphy. Hydration of volcanic glass from Leg 57 is less intense than in other DSDP cores.

Siliceous components of Pliocene-Holocene sediments of the South Atlantic

The Pliocene-Holocene sediments recovered on ODP Leg 114 from Holes 699A, 701C, and 704B are the subject of a detailed investigation to interpret changes in the Oceanographic environment of the South Atlantic in the vicinity of the Polar Front Zone (PFZ). The cores sample sediments at shallow (Hole 704B, 2532 m), intermediate (Hole 699A, 3716 m), and basinal (Hole 701C, 4647 m) depths. Sites 699 and 704 come under the influence of the Antarctic Circumpolar Current (ACC) and Circumpolar Deep Water. It is possible that the upper reaches of Antarctic Bottom Water (AABW) may also affect Hole 699A. Site 701 is influenced by AABW. Closely spaced samples were analyzed for grain-size distribution, sand fraction components, biosiliceous microfossils, organic carbon, and water content. PFZ migrations are traced using changes in bulk sedimentaccumulation rates and the abundance of the diatoms Actiniscus ssp. and Genus et species indet. 1 Fenner (1991), as well as changes in sediment grain size and composition. Diatomaceous sediments of Gilbert age in Hole 699A indicate that the PFZ was positioned over this site, but during the Gauss it migrated north, bringing in less productive Antarctic Surface Water. All cores document a very gradual southerly movement of the PFZ throughout the Matuyama (with some sharp fluctuations of the northen PFZ border over Site 704 between 1.45 and 1.83 m.y.). This regressive shift culminated in the late Matuyama. The latest Matuyama to earliest Brunhes record in Hole 699A has been removed by a hiatus lasting from 1.0 to 0.6 m.y., which was probably caused by intensification of the deep-reaching ACC. The corresponding interval in Hole 704B, the shallowest core, contains evidence of winnowing. Sharp fluctuations of large amplitude and high frequency in the lithology of the sediments from Hole 704B in the eastern South Atlantic, starting at about 0.75 m.y. and characterizing the whole Brunhes Epoch, record the rapid movement of the northern border of the PFZ over the site. These reflect strong glacial/interglacial alternations in climate. To a lesser extent, lithologic fluctuations in Hole 701C reflect the same phenomenon, whereas in Hole 699A the lithology does not vary as dramatically.

Oxygen, carbon and strontium isotope data for DSDP Hole 35-323

A downhole decrease in 18O, Mg(2+) and K+, an increase in Ca(2+) and a low 87Sr/86Sr ratio of 0.7067 in the pore fluids of DSDP site 323 were caused principally by the alteration of volcanic material. These chemical and isotopic patterns were produced by the alteration, in order of decreasing importance of: a 60-m thick basal layer of volcanic ash; the underlying basalts; and igneous components in the 640-m thick upper sequence composed largely of terrigenous material. A significant portion of the alteration of the ash in the basal sequence must have occurred before the deposition of the upper sediments, perhaps under the influence of advecting solutions. The rest of the alteration occurred during the deposition of the thick upper sediments. Mass balance considerations and the low d18O values of most of the alteration products suggest that much of the later alteration occurred progressively over the last 13 Myr. The principal alteration products were smectite, potassium feldspar, clinoptilolite and calcite.

(Table 1) Geochemistry of upper Paleocene and upper Eocene glass particles at DSDP Hole 80-549

Two ash horizons have been identified in Hole 549, one in the upper Paleocene (basal NP9), the other in the upper Eocene (NP18); both are mixed lithic crystal tuffs of rhyolitic composition. These tuffs are absent in Hole 550 owing to unconformities, but the basal Eocene (NP10) of Hole 550 includes a series of over 50 thin bentonite layers. Intermediate plagioclase associated with these bentonites indicates that the original ash was of basaltic to andesitic composition. The bentonites are absent in Hole 549, probably because of an unconformity, but they have been identified in Hole 401 (Leg 48, Bay of Biscay). Two of the pyroclastic phases can be matched with phases previously reported for the North Sea Basin. The bentonites of Site 550 are probably equivalent to the widespread "ash series" of northwestern Europe, which may therefore be regarded as being lower Eocene in terms of Martini's calcareous nannoplankton zonation.