Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Stable carbon and oxygen isotope record of planktonic foraminifera in ODP Site 138-851

This study investigates changes in the upper water column hydrography at Site 851 of the eastern tropical Pacific Ocean since the late Pliocene, using the oxygen and carbon isotopic composition of three species of planktonic foraminifers, each calcifying at different depths in the photic zone. The upper ocean seasonal hydrography in this region responds to the seasonally changing trade winds and thus is expected to respond to past changes in trade winds. One major change occurs at about 1.5 Ma, when the thermocline adjusts from a deep position to a shallower position. The thermocline remains in a relatively shallow position throughout the record up to recent time, with slight variations occurring synchronously with glacial/interglacial stages. In glacials, SSTs are probably a few degrees cooler and the thermocline is slightly deeper. From our knowledge of seasonal and interannual adjustments of the thermocline in this location, a deeper thermocline might be interpreted as either a decrease in the strength of the Equatorial Undercurrent (EUC) that results from lower mean wind strength or an increase in the Equatorial Countercurrent (ECC), which results from an increase in the strength of the southeasterly trade winds. A major shift from higher to lower carbon isotope values occurred at about 1.9 Ma, marking a transition to reduced planktonic-benthic d13C differences after 1.9 Ma. The carbon isotopic data indicate that changes in the carbon isotopic composition of intermediate upwelling water occurs at higher frequencies than the glacial/interglacial changes in ice volume.

Stable carbon and oxygen isotope ratios of benthic foraminifera from Paleocene to Oligocene sediments

Benthic oxygen and carbon isotopic results from a depth transect on Maud Rise, Antarctica, provide the first evidence for Warm Saline Deep Water (WSDW) in the Paleogene oceans. Distinct reversals occur in the oxygen isotopic gradient between the shallower Hole 689B (Eocene depth ~1400 m; present-day depth 2080 m) and the deeper Hole 690B (Eocene depth ~2250 m; present-day depth 2914 m). The isotopic reversals, well developed by at least 46 Ma (middle middle Eocene), existed for much of the remaining Paleogene. We do not consider these reversals to be artifacts of differential diagenesis between the two sites or to have resulted from other potentially complicating factors. This being so, the results show that deep waters at Hole 690B were significantly warmer than deep waters at the shallower Hole 689B. A progressive decrease and eventual reversal in benthic to planktonic delta18O gradients in Hole 690B, demonstrate that the deeper waters became warmer relative to Antarctic surface waters during the Eocene. The warmer deep waters of the Paleogene are inferred to have been produced at middle to low latitudes, probably in the Tethyan region which contained extensive shallow-water platforms, ideal sites for the formation of high salinity water through evaporative processes. The ocean during the Eocene, and perhaps the Paleocene, is inferred to have been two-layered, consisting of warm, saline deep waters formed at low latitudes and overlain by cooler waters formed at high latitudes. This thermospheric ocean, dominated by halothermal circulation we name Proteus. The Neogene and modern psychrospheric ocean Oceanus is dominated by thermohaline circulation of deep waters largely formed at high latitudes. An intermediate condition existed during the Oligocene, with a three-layered ocean that consisted of cold, dense deep waters formed in the Antarctic (Proto-AABW), overlain by warm, saline deep waters from low latitudes, and in turn overlain by cool waters formed in the polar regions. This we name Proto-oceanus which combined both halothermal and thermohaline processes. The sequence of high latitude, major, climatic change inferred from the oxygen isotopic records is as follows: generally cooler earlier Paleocene; warming during the late Paleocene; climax of Cenozoic warmth during the early Eocene and continuing into the early middle Eocene; cooling mainly in a series of steps during the remainder of the Paleogene. Superimposed upon this Paleogene pattern, the Paleocene/Eocene boundary is marked by a brief but distinct warming that involved deep to surface waters and a reduction in surface to deep carbon and oxygen isotopic gradients. This event coincided with major extinctions among the deep-sea benthic foraminifers as shown by Thomas (1990 doi:10.2973/odp.proc.sr.113.123.1990). Salinity has played a major role in deep ocean circulation, and thus paleotemperatures cannot be inferred directly from the oxygen isotopic composition of Paleogene benthic foraminifers without first accounting for the salinity effect.

Biostratigraphy and Sr isotopic composition of sediments from DSDP Legs 12, 14, 15, 17, 20-22, and 30

We present the data used to construct the Cenozoic and Cretaceous portion of the Phanerozoic curve of seawater 87Sr/86Sr that had been given in summary form by W.H. Burke co-workers. All Cenozoic samples (128) and 22 Cretaceous samples are foram-nannofossil oozes and limestones from DSDP cores distributed among 13 sites in the Atlantic, Pacific and Indian Oceans, and the Caribbean Sea. Non-DSDP Cretaceous samples (126) include limestone, anhydrite and phosphate samples from North America, Europe and Asia. Determination of the 87Sr/86Sr value of seawater at particular times in the past is based on comparison of ratios derived from coeval marine samples from widely separated geographic areas. These samples are characterized by a wide variety of diagenetic and burial histories. The large size and cosmopolitan nature of the data set decreases the likelihood that, among coeval data, systematic error has been introduced by a similar pattern of diagenetic alteration of the ratios. There is good clustering of data points throughout the Cenozoic and Cretaceous curve. The consistency of data is illustrated by Cenozoic and Cretaceous data plots that include a separate symbol for each DSDP site and non-DSDP sample location. More than 98% of the data points are enclosed by upper and lower lines that define a narrow band. For any given time, the correct seawater ratio probably lies within this band. A line drawn within the band represents our estimate of the actual seawater ratio as a function of time. The general configuration of the Cenozoic and Cretaceous curve appears to be strongly influenced by the history of plate interactions and sea-floor spreading. Specific rises and falls in the 87Sr/86Sr of seawater, however, may be caused by a variety of factors such as variation in lithologic composition of the crust exposed to weathering, configuration and topographic relief of continents, volcanic activity, rate of sea-floor spreading, extent of continental inundation by epeiric seas, and variations in both climate and paleooceanographic conditions. Many or all of these factors are probably related to global tectonic processes, yet their combined effect on the temporal variation of seawater 87Sr/86Sr can complicate a direct platetectonic interpretation for portions of the seawater curve.

Composition of dikes and lavas from the Pito Deep Rift

The northwest trending walls of the Pito Deep Rift (PDR), a tectonic window in the southeast Pacific, expose in situ oceanic crust generated ?3 Ma at the superfast spreading southern East Pacific Rise (SEPR). Whole rock analyses were performed on over 200 samples of dikes and lavas recovered from two ~8 km**2 study areas. Most of the PDR samples are incompatible-element-depleted normal mid-ocean ridge basalts (NMORB; (La/Sm)N < 1.0) that show typical tholeiitic fractionation trends. Correlated variations in Pb isotope ratios, rare earth element patterns, and ratios of incompatible elements (e.g., (Ce/Yb)N) are best explained by mixing curves between two enriched and one depleted mantle sources. Pb isotope compositions of most PDR NMORB are offset from SEPR data toward higher values of 207Pb/204Pb, suggesting that an enriched component of the mantle was present in this region in the past ?3 Ma but is not evident today. Overall, the PDR crust is highly variable in composition over long and short spatial scales, demonstrating that chemically distinct lavas and dikes can be emplaced within the same segment over short timescales. However, the limited spatial distribution of high 206Pb/204Pb samples and the occurrence of relatively homogeneous MgO compositions (ranging <2.5 wt %) within a few of the individual dive transects (over distances of ~1 km) suggests that the mantle source composition evolved and magmatic temperatures persisted over timescales of tens of thousands of years. The high degree of chemical variability between pairs of adjacent dikes is interpreted as evidence for along-axis transport of magma from chemically distinct portions of the melt lens. Our findings suggest that lateral dike propagation occurs to a significant degree at superfast spreading centers.

(Table 1) Sulfur content and sulfur-isotope ratios at DSDP Leg 82 Holes basalts

The sulfur contents of 21 basalt samples from four DSDP Leg 82 holes were determined and the isotopic compositions of sulfur were measured on 15 of them. Most of the basalts are altered and have sulfur contents of about 100 ppm. Isotopic ratios for sulfate and total sulfur range from +0.7 to +10.5 per mil, indicating almost complete leaching of the igneous sulfide in low-sulfur samples by alteration. Total sulfur content of some samples ranges between 960 and 1170 ppm, somewhat higher than expected for tholeiitic basalts. The isotope ratios of total sulfur in these samples are slightly shifted to values heavier than the generally assumed mantle ratio of zero, and this shift is thought to result from a secondary source of sulfur.

Nd and Pb isotope data for DSDP and ODP sediments from the Bengal Fan

Correlation of new multichannel seismic profiles across the upper Indus Fan and Murray Ridge with a dated industrial well on the Pakistan shelf demonstrates that ~40% of the Indus Fan predates the middle Miocene, and ~35% predates uplift of the Murray Ridge (early Miocene, ~22 Ma). The Arabian Sea, in addition to the Makran accretionary complex, was therefore an important repository of sediment from the Indus River system during the Paleogene. Channel and levee complexes are most pronounced after the early Miocene, coincident with an increase in sedimentation rates. Middle Eocene sandstones from Deep Sea Drilling Project Site 224 on the Owen Ridge yield K-feldspars whose Pb isotopic composition, measured by in situ ion microprobe methods, indicates an origin in, or north of, the Indus suture zone. This observation requires that India-Asia collision had occurred by this time and that an Indus River system, feeding material from the suture zone into the basin, was active soon after collision. Pleistocene provenance was similar to that during the Eocene, albeit with greater contribution from the Karakoram. A mass balance of the erosional record on land with deposition in the fan and associated basins suggests that only ~40% of the Neogene sediment in the fan is derived from the Indian plate.

(Table 1) Oxygen and carbon isotope compositions of altered carbonates from DSDP Hole 6-53 from the western Pacific Ocean

In the lower part of DSDP core 53.0, partly recrystallized carbonate sediments and well recrystallized limestone breccias of Oligo-Miocene age are associated with altered volcanic flows, lithified tuffs, and tuff breccias, suggesting that carbonate alteration was the result of thermal metamorphism. However, the oxygen isotope compositions of these carbonates (-3.4 to +0.6 per mil rel. PDB) are not compatible with recrystallization and isotope exchange with sea water at high temperatures. Evaluating the effects of the composition of the water which exchanged with the carbonates and of carbonate-water isotope exchange in closed systems yields the following approximate maximum temperature of recrystallization: limestone breccias, 100°C; calcite veins rimming breccia clasts, 30°C; and unconsolidated sediments overlying the breccias, 20°C. Therefore, the volcanics at site 53.0 must have been emplaced into the primary carbonate sediments at relatively low temperatures. Subsequent carbonate alteration was probably a consequence of chemical changes in ambient pore waters resulting from the submarine weathering of volcanic material.

Os and Re concentrations and Os isotope ratios for DSDP and ODP metalliferous sediments from the Pacific Ocean (Table 1)

We report new 187Os/186Os data and Re and Os concentrations in metalliferous sediments from the Pacific to construct a composite Os isotope seawater evolution curve over the past 80 m.y. Analyses of four samples of upper Cretaceous age yield 187Os/186Os values of between 3 and 6.5 and 187Re/186Os values below 55. Mass balance calculations indicate that the pronounced minimum of about 2 in the Os isotope ratio of seawater at the K-T boundary probably reflects the enormous input of cosmogenic material into the oceans by the K-T impactor(s). Following a rapid recovery to 187Os/186Os of 3.5 at 63 Ma, data for the early and middle part of the Cenozoic show an increase in 187Os/186Os to about 6 at 15 Ma. Variations in the isotopic composition of leachable Os from slowly accumulating metalliferous sediments show large fluctuations over short time spans. In contrast, analyses of rapidly accumulating metalliferous carbonates do not exhibit the large oscillations observed in the pelagic clay leach data. These results together with sediment leaching experiments indicate that dissolution of non-hydrogenous Os can occur during the hydrogen peroxide leach and demonstrate that Os data from pelagic clay leachates do not always reflect the Os isotopic composition of seawater. New data for the late Cenozoic further substantiate the rapid increase in the 187Os/186Os of seawater during the past 15 Ma. We interpret the correlation between the marine Sr and Os isotope records during this time period as evidence that weathering within the drainage basin of the Ganges-Brahmaputra river system is responsible for driving seawater Sr and Os toward more radiogenic isotopic compositions. The positive correlation between 87Sr/86Sr and U concentration, the covariation of U and Re concentrations, and the high dissolved Re, U and Sr concentrations found in the Ganges-Brahmaputra river waters supports this interpretation. Accelerating uplift of many orogens worldwide over the past 15 Ma, especially during the last 5 Ma, could have contributed to the rapid increase in 187Os/186Os from 6 to 8.5 over the past 15 Ma. Prior to 15 Ma the marine Sr and Os record are not tightly coupled. The heterogeneous distribution of different lithologies within eroding terrains may play an important role in decoupling the supplies of radiogenic Os and Sr to the oceans and account for the periods of decoupling of the marine Sr and Os isotope records.

U-Pb, trace element, and Hf isotope analysis for Macquarie Island detrital zircon

Oceanic zircon trace element and Hf-isotope geochemistry offers a means to assess the magmatic evolution of a dying spreading ridge and provides an independent evaluation of the reliability of oceanic zircon as an indicator of mantle melting conditions. The Macquarie Island ophiolite in the Southern Ocean provides a unique testing ground for this approach due to its formation within a mid-ocean ridge that gradually changed into a transform plate boundary. Detrital zircon recovered from the island records this change through a progressive enrichment in incompatible trace elements. Oligocene age (33-27 Ma) paleo-detrital zircon in ophiolitic sandstones and breccias interbedded with pillow basalt have trace element compositions akin to a MORB crustal source, whereas Late Miocene age (8.5 Ma) modern-detrital zircon collected from gabbroic colluvium on the island have highly enriched compositions unlike typical oceanic zircon. This compositional disparity between age populations is not complimented by analytically equivalent eHf data that primarily ranges from 14 to 13 for sandstone and modern-detrital populations. A wider compositional range for the sandstone population reflects a multiple pluton source provenance and is augmented by a single cobble clast with eHf equivalent to the maximum observed composition in the sandstone (~17). Similar sandstone and colluvium Hf-isotope signatures indicate inheritance from a similar mantle reservoir that was enriched from the depleted MORB mantle average. The continuity in Hf-isotope signature relative to trace element enrichment in Macquarie Island zircon populations, suggests the latter formed by reduced partial melting linked to spreading-segment shortening and transform lengthening along the dying spreading ridge.

Sediment composition and sedimentation rates of four Holes in ODP Leg 166

To date, work on the Great Bahama Bank's western, leeward margin has centred chiefly on seismic-scale expressions of carbonate sequences and systems tracts. However, periplatform, slope sediments also exhibit very well developed cyclicity on scales of decimetres to several metres. It is these small-scale, high-frequency cycles within the larger-scale facies successions of the Quaternary which form the main topic of this paper. Previous studies have shown that the small-scale cycles correlate to the orbitally forced, high-frequency sea-level changes. Therefore these cycles should indicate how sea level has affected the slope development and thus platform-margin evolution during this period. Through detailed, high-resolution sequence stratigraphy of the Great Bahama Bank's leeward margin, obtained via delta18O isotope and mineralogical (XRD) analyses, confined by U/Th dating and nannofossil bioevents, a greater understanding of the bedding geometries within the Pleistocene-Holocene seismic sequences and clues as to the nature of the slope development has been achieved. The high-resolution seismic profiles indicate that since the Plio-Pleistocene change in geometry, in which the Great Bahama Bank developed into a rimmed platform, continued steepening and subsequent progradation of the leeward margin has typified slope development during the Quaternary, which is described as an accretionary slope. However, on the basis of our observations we conclude that only the early to lower middle Pleistocene section (isotope stages 45-20) and the Holocene (isotope stage 1) of the leeward margin is accretionary. This indicates that a degree of erosion and/or by-passing has occurred on the leeward margin since the lower middle Pleistocene (isotope stage 19). During the first part of this period (isotope stages 19-12) erosion and/or by-passing occurred in the middle to lower slope regions and toe-of-slope. By the end of the upper middle to late Pleistocene phase (isotope stages 11-2) erosion also occurred on the upper slope. This erosion by currents at the toe-of-slope and oversteepening of the upper and middle slopes have led to back-cutting upslope and resulted in the progressive retreat of the toe-of-slope towards the platform to the east. However, the rise in sea level since the Last Glacial Maximum to its present-day level has allowed high productivity on the platform top during the Holocene and the deposition of a thick sediment wedge on the slope and sedimentation across the entire leeward flanks. This has led to the redevelopment of an accretionary slope and continued westward progradation of the Great Bahama Bank's western, leeward margin.