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.

Origin and evolution of Cycladophora davisiana (Radiolaria) in DSDP Hole 19-192, Northwest Pacific

This paper documents the evolutionary history of Cycladophora davisiana Ehrenberg from an uppermost Miocene to Pleistocene sedimentary record in the high-latitude Northwest Pacific. It apparently evolved from C. sakaii Motoyama through a series of intermediates. C. sakaii has a relatively large shell with an external spongy layer. The evolutionary transition is characterized by a relatively rapid decrease in thorax size with a reduction of the spongy appendage. This change occurred during about 0.4 m.y. from 2.8 to 2.4 Ma without cladogenesis. Following this interval, a decrease in thorax size continued gradually up to the Recent, resulting in a very small morphology. Although the population of C. davisiana first appeared at about 2.5 Ma, some morphotypic specimens may occur in earlier periods as indistinguishable very small endmembers in the C. sakaii populations. Timing of the first appearance events both of morphotypic specimens and of a population of C. davisiana in Site 192 and previously reported cores does not disprove the idea that C. davisiana evolved first in the Northwest Pacific region, and later migrated into other regions of the world ocean. Biometrics clearly indicate no direct phylogenetic relationships between C. davisiana and C. cornutoides Kling in the studied core. Thus, the latter species, which was originally described as a variation and later elevated to a subspecies of the former species, is separated from the former species and raised to the species rank.

Distribution of Cycladophora davisiana davisiana in upper Pliocene and Pleistocene sediments of the North Atlantic and Labrador Sea

Upper Pliocene and Pleistocene abundance fluctuations of the radiolarian Cycladophora davisiana (Ehrenberg) davisiana (Petrushevskaya) are documented from North Atlantic (Site 609) and Labrador Sea (Site 646B) to provide the first long-term correlation of its abundance fluctuations to oxygen isotope stages 1-114. Also examined are temporal and regional fluctuations in abundances C. d. davisiana and the global dispersal routes of the species. The first occurrence of C. d. davisiana in the eastern North Atlantic Ocean (Site 609) occurred between 2.586 and 2.435 Ma (oxygen isotope stages 109.66-102.19). During the early Matuyama Chron, prior to oxygen isotope stage 63, C. d. davisiana abundances were less than 1% and never greater than 12%, while abundances of greater than 5% are found in stages 65.71-73, 74, and 83-84. The initial major abundance peak (35.7%) of C. d. davisiana was noted near the stage 63/62 boundary. Abundance peaks of greater than 15%, between oxygen isotope stages 35 and 63, are limited to stages 63.02, 58.07, 55.07-54.26, and 50.76-50.22. These represent the only such abundance peaks detected during the first c. 1.5 million years of the species within the North Atlantic. The character of C. d. davisiana abundance fluctuations in Site 609 changes after oxygen isotope stage 35; average abundances are greater (7.7% vs. 4.3%) and abundance maxima of more than 15% are more frequent. Many, but not all, peak abundances of C. d. davisiana occur in glacial stages (e.g., 8, 14, 18, 20, 26, 30, 34, 50, 54, and 58). Increased abundances of the species are also noted in weak interglacial stages (e.g., stages 3, 23, 39, and 41), and significant cool periods of robust interglacial periods (e.g., late stage 11). Sample spacing is adequate in some stages to note some rapid changes in abundance near stage transitions (e.g., stages 4/5, 25/26, 62/63). The sample density in Holes 609 and 611 and the upper portion of 646B is sufficient to detect a synchroneity of many abundance maxima and minima among sites. Some abundance peaks are undetected in one or more of the two holes, warranting further sampling to obtain a more accurate record of regional abundance fluctuations. Prior to stage 36, few ages of Hole 611 peaks are the same as those in the more precisely dated Hole 609. The highest abundances of C. d. davisiana were noted in Labrador Sea Hole 646B where the earliest known occurrence of the species is documented (3.08-2.99 Ma). C. d. davisiana is inferred to have evolved in the Labrador Sea (or Arctic), and migrated next through the Arctic into the North Pacific (2.62-2.64 Ma, stage 114) before migrating into the Norwegian Sea (2.63-2.53 Ma) and North Atlantic (2.59-2.44 Ma, stages 109-102). Additional migration of C. d. dauisiana into the southern South Atlantic (Site 704) occurred much later (2.06 Ma, stage 83).

Sulphur contents and partition of iron in ODP Leg 112 sediments

Porewaters in site 680 Peru Margin sediments contain dissolved sulfide over a depth of approximately 70 m which, at a sedimentation rate of 0.005 cm/yr, gives a sediment exposure time to dissolved sulfide of about 1.4 Myr. Reactions with dissolved sulfide cause the site 680 sediments to show a progressive decrease in a poorly-reactive silicate iron fraction, defined as the difference between iron extracted by dithionite (FeD) at room temperature and that extracted by boiling concentrated HCl (FeH), normalised to the total iron content (FeT). Straight line plots are obtained for ln[(FeH - FeD)/FeT] against time of burial, from which a first order rate constant of 0.29 1/Myr (equivalent to a half-life of 2.4 Myr) can be derived for the sulfidation of this silicate iron. Comparable half-lives are also found for the same poorly-reactive iron fraction in the nearby site 681 and 684 sediments. This silicate Fe fraction comprises 0.8-1.0% Fe, only 30-60% of which reacts even with 1.5-3 million years exposure to dissolved sulfide. Diagenetic models based on porewater concentrations of sulfate and sulfide, and solid phase iron contents, at site 680 are consistent in indicating that this poorly-reactive iron fraction is only sulfidized on a million year time scale. Silicate iron not extracted by HCl can be regarded as unreactive towards dissolved sulfide on the time scales encountered in marine sediments.

Occurrence of radiolarians in DSDP Hole 11-98 (Table 1)

Site 634, drilled during ODP Leg 101, was essentially a reoccupation of Site 98, drilled during DSDP Leg 11 (Hollister, Ewing, et al., 1972, doi:10.2973/dsdp.proc.11.1972; Table 1, Fig. 1). At Site 634, the upper 144 m of sediment was washed in an attempt to reach the Upper Cretaceous target horizon in the time remaining for the cruise (Austin, Schlager, et al., 1986, doi:10.2973/odp.proc.ir.101.1986). Figure 2 illustrates the spatial relationship of Site 98 (2750 m water depth) and Site 634 (2835 m water depth), 0.2 nmi to the northwest. Radiolarians were observed in Site 98 samples from 100 to 240 meters below seafloor (mbsf) during Leg 11, but no detailed biostratigraphic analyses were conducted. Thus, Site 98 presented us an opportunity to sample material correlating with the washed section at Site 634. Samples were taken from Cores 101-634A-2R through 101-634A-4R to study radiolarians, but all proved barren, nor were radiolarians observed in shipboard smear slides. A correlation between Sites 98 and 634 (Fig. 2) suggests that these cores represent the same interval as that recovered in Cores 11-98-10 and 11-98-11, which were also barren. These results are presented separately from other Leg 101 radiolarian studies (Palmer, 1988, datasets: doi:10.1594/PANGAEA.743055) because the Site 98 fauna was predominantly Eocene, while other radiolarian assemblages studied were Oligocene and Miocene.

Geochemistry of ODP Site 135-834 basalts

New major, trace element, and isotope data (Pb, Sr, and Nd) reveal an impressive compositional variation in the basalts recovered from Site 834. Major element compositions span almost the entire range observed in basalts from the modern axial systems of the Lau Basin, and variations are consistent with low-pressure fractionation of a mid-ocean-ridge-basalt (MORB)-like parent, in which plagioclase crystallization has been somewhat suppressed. Trace element compositions deviate from MORB in all but one unit (Unit 7) and show enrichments in large-ion-lithophile elements (LILEs) relative to high-field-strength elements (HFSEs) more typically associated with island-arc magmas. The Pb-isotope ratios define linear trends that extend from the field of Pacific MORB to highly radiogenic values similar to those observed in rocks from the northernmost islands of the Tofua Arc. The Sr-isotope compositions also show significant variation, and these too project from radiogenic values back into the field for Pacific MORB. The variations in key trace element and isotopic features are consistent with magma mixing between two relatively mafic melts: one represented by Pacific MORB, and the other by a magma similar to those erupted on 'Eua when it was part of the original Tongan arc, or perhaps members of the Lau Volcanic Group (LVG). Based on our model, the most radiogenic compositions (Units 2 and 8) represent approximately 50:50 mixtures of these MORB and arc end-members. Magma mixing requires that both components are simultaneously available, and implies that melts have not shown a compositional progression from arc-like to MORB-like with extension at this locality. Rather, it is apparent that essentially pristine MORB can erupt as one of the earliest products of backarc initiation. Indeed, repetition of isotopic and trace element signatures with depth suggests that eruptions have been triggered by periodic injections of fresh MORB melts into the source regions of these magmas. The slow and almost amagmatic extension of the original arc complex envisaged to explain the observed chemistry is also consistent with the horst-and-graben topography of the western side of the Lau Basin. Given the similarities between basalts erupted at the modern Lau Basin spreading centers and MORB from the Indian Ocean, the overwhelming evidence for involvement of mantle similar to Pacific MORB in the petrogenesis of basalts from Site 834 is a new and important observation. It indicates that the original arc was underlain by asthenospheric material derived from the Pacific mantle convection cell, and that this has somehow been replaced by Indian Ocean MORB during the last ~5.5 Ma.

Occurrence and isotopic composition (d18O, d13C) of benthic foraminifera in sediments from DSDP Leg 72

Changes in the vertical water mass structure of the Vema Channel during the Pliocene have been inferred from benthic foraminiferal assemblages and stable isotopic analyses from three sites of DSDP Leg 72 (South Atlantic). Faunal and isotopic results from Sites 516A and 518 suggest that a major change occurred in deep-water circulation patterns in the late Pliocene near 3.2 Ma. Benthic oxygen isotopic records from Sites 516A and 518 show a characteristic increase in d18O values near 3.2 Ma. This has been documented in numerous Pliocene isotopic records. The magnitude of the oxygen isotopic enrichment near 3.2 Ma appears to increase with water depth from an average enrichment of 0.34 per mil in Site 516A (1313 m) to an average enrichment of 0.58 per mil in Site 518 (3944 m). We suggest that this enrichment resulted partly from a change in deep-water circulation patterns which included a decrease in bottom-water temperatures. Planktonic d18O values near 3.2 Ma show no evidence of an enrichment which would be indicative of an increase in global ice volume. On the contrary, d18O values in Sites 517 and 518 become more depleted near 3.2 Ma, indicating a surface-water warming perhaps due to a change in the strength and/or position of the Brazil Current. An increase in the relative abundance of the benthic foraminifer Nuttalides umbonifera, which is associated with Antarctic Bottom Water (AABW) in the modern ocean, coincides with the benthic 18O enrichment in Site 518. At 3.2 Ma, oxygen and carbon isotopic gradients between Sites 518 (3944 m) and 516A (1313 m) show a marked increase such that Site 518 becomes enriched in 18O and depleted in 13C relative to Site 516A. This enrichment in d18O is interpreted as partly representing a temperature decrease at Site 518; the depletion in d13C indicates a corrosive water mass which is high in metabolic CO2. We suggest that benthic foraminiferal and stable isotopic changes in Site 518 resulted from a pulse-like increase in the formation of AABW near 3.2 Ma. The cause of this circulation event may have been linked to global cooling and/or the final closure of the Central American Seaway.

Stable isotopc record of ODP Site 114-704

We report a near-continuous, stable isotopic record for the Pliocene-Pleistocene (4.8 to 0.8 Ma) from Ocean Drilling Program Site 704 in the sub-Antarctic South Atlantic (47°S, 7°E). During the early to middle Pliocene (4.8 to 3.2 Ma), variation in delta18O was less than ~0.5 per mil, and absolute values were generally less than those of the Holocene. These results indicate some warming and minor deglaciation of Antarctica during intervals of the Pliocene but are inconsistent with scenarios calling for major warming and deglaciation of the Antarctic ice sheet. The climate System operated within relatively narrow limits prior to ~3.2 Ma, and the Antarctic cryosphere probably did not fluctuate on a large scale until the late Pliocene. Benthic oxygen isotopic values exceeded 3 per mil for the first time at 3.16 Ma. The amplitude and mean of the delta18O signal increased at 2.7 Ma, suggesting a shift in climate mode during the latest Gauss. The greatest delta18O values of the Gaus anti Gilbert chrons occurred at ~2.6 Ma, just below a hiatus that removed the interval from ~2.6 to 2.3 Ma in Site 704. These results agree with those from Subantarctic Site 514, which suggest that the latest Gauss (2.68 to 2.47 Ma) was the time of greatest change in Neogene climate in the northern Antarctic and Subanthtic regions. During this period, surface water cooled as the Polar Front Zone (PFZ) migrated north and perennial sea ice Cover expanded into the Subantarctic region. Antarctic ice volume increased and the ventilation rate of Southern Ocean deep water decreased during glacial events after 2.7 Ma. We suggest that these changes in the Southern Ocean were related to a gradual lowering of sea level and a reduction in the flux of North Atlantic Deep Water (NADW) with the Initiation of ice growth in the northern hemisphere. The early Matuyama Chron (~ 2.3 to 1.7 Ma) was marked by relatively warm climates in the Southern Ocean except for strong glacial events associated with isotopic stages 82 (2.027 Ma), 78 (1.941 Ma), and 70 (1.782 Ma). At 1.67 Ma (stage 65/64 transition), surface waters cooled as the PFZ migrated equatorward and oscillated about a far northerly position for a prolonged interval between 1.67 and 1.5 Ma (stages 65 to 57). Beginning at ~1.42 Ma (stage 52), all parameters (delta18O, delta13C, %opal, %CaCO3) in Hole 704 become highly correlated with each other and display a very strong 41-kyr cyclicity. This increase in the importance of the 41-kyr cycle is attributed to an increase in the amplitude of the Earth's obliquity cycle that was likely reinforced by increased glacial suppression of NADW, which may explain the tightly coupled response that developed between the Southern Ocean and the North Atlantic beginning at ~1.42 Ma (stage 52).

Sediment description, CaCO3, density and porosity at DSDP Site 89-585

Siliceous sediments and sedimentary rocks occur as chert and silicified chalk, limestone, and claystone in Site 585 lower Miocene to Campanian sediments, with one older occurrence of chert near the Cenomanian/Turonian boundary. The recovered drill breccia in the Miocene to middle Eocene interval is dominated by bright red, orange, yellow, and brown chips and fragments of chert. In early Eocene and older sediments gray silicified limestone and yellowish brown chert fragments predominate. Recovery is poor in cores with chert because chert tends to fracture into smaller pieces that escape the drill and because the hard chert fragments grind away other sediments during rotary drilling. Thin-section and hand-sample studies show complex diagenetic histories of silicification (silica pore infill) and chertification (silica replacement of host rock). Multiple events of silicification can occur in the same rocks, producing chert from silicified limestone. Despite some prior silicification, silicified limestone is porous enough to provide conduits for dissolved silica-charged pore waters. Silicification and chert are more abundant in the coarser parts of the sedimentary section. These factors reflect the importance of porosity and permeability as well as chemical and lithologic controls in the process of silica diagenesis.

(Table 1) Platinum group element abundanves in ODP Leg 135 samples

Ocean Drilling Program Leg 135 backarc basin lavas are characterized by anomalously high Au contents (1.0-11.4 ppb) and strongly fractionated relative platinum group element (PGE) abundances (Pd/Ir ratio, approximately 100). The Rh and Ir contents are very low, ranging from below detection (approximately 0.02 ppb) to 0.08 ppb. The Pd and Pt contents range from <0.3 to 4 ppb. Rh, Pd, and Pt values are consistently and significantly higher in Site 836 and 839 samples relative to those from Sites 834 and 835. Major, trace, and rare earth element (REE) data suggest Sites 836 and 839 have a more pronounced arc signature than Sites 834 and 835. No correlation exists between noble metal abundance and indices of alteration or fractionation (e.g., loss on ignition (LOI), Mg#, and Cr or Ni contents), suggesting that measured values and ratios are primary and reflect characteristics of the mantle source. The evaluation of Leg 135 noble metal data with respect to potential mantle-source components is hindered by the lack of data on magmas derived from such sources. However, analyses of the limited available data for the different magma types suggest that the characteristic enrichment of Leg 135 lavas in Au, relative to Pd and Cu, cannot be derived solely from simple MORB-type or ocean-island-type mantle, or mantle depleted by a previous melt extraction event. The Au-enriched signature of the Lau basin lavas could, however, be produced through the addition of a sedimentary component from the downgoing slab. Separation of Au from the PGE occurs within oceanic hydrothermal systems and gold values of the resultant precipitates are 2-3 orders of magnitude higher than other oceanic crustal components. Even small additions of this component from the downgoing oceanic crust to a supra-subduction zone mantle melt could account for the high mean Au/Pd ratios of the Leg 135 samples (Sites 834 and 835, Au/Pd = 5.04; Sites 836 and 839, Au/Pd = 2.26).

Minerals and geochemistry abundance and occurance, as well as K-Ar determinations for DSDP Site 92-597 basalts

Preliminary studies of hydrothermally altered massive basalts formed at the fast-spreading Mendoza Rise and recovered from DSDP Holes 597B and 597C indicate the presence of three secondary mineral assemblages which formed in the following order: (1) trioctahedral chlorite and talc, (2) goethite and smectite, and (3) calcite and celadonite. The sequential precipitation of these mineral assemblages denotes high water:rock ratios and time-varying conditions of temperature (early >200°C to late <30°C) and state of oxidation (early nonoxidative to late oxidative). A decrease in the relative proportion of oxidative mineral assemblages with depth to 70 m in Site 597 basement indicates a zone of oxidative alteration that became shallower with time as the deeper, more constricted fracture systems were filled by secondary mineralization. In this report we present the first results of the K-Ar dating of celadonite formation age; celadonite formation reflects end-stage hydrothermal alteration in Site 597 basement. Three celadonite dates obtained from Site 597 samples include 13.1 ± 0.3 m.y. from 17 m basement depth (Hole 597B), 19.9 ± 0.4 m.y. from 18 m basement depth (Hole 597C), and 19.3 ± 1.6 m.y. from 60 m basement depth (Hole 597C). The age of host rock crystallization (28.6 m.y.) and the K-Ar dates of celadonite formation establish that hydrothermal alteration in the upper 70 m of Site 597 basement continued for at least 10 m.y. and possibly as long as 16 m.y. after basalt crystallization at the ridge crest. Assuming a half-spreading rate of 55 km/m.y., we calculate that hydrothermal circulation was active in shallow basement at a distance of at least 550 km off ridge crest and possibly as far as 1000 km off ridge crest.

Nannofossil and planktic foraminiferal events of ODP Site 166-1006 sediments

Detailed biostratigraphy in Site 1006 based on planktonic foraminifers and nannofossils shows large-scale sedimentation rate variability in the Florida Strait west of the Great Bahama Bank. A 'floating' cyclostratigraphy based mainly on resistivity logs and magnetic susceptibility data has been fixed to the biostratigraphy in the absence of magnetostratigraphy. The strongest orbital cycle present is the precessional beat, which is present in the borehole logs throughout the record. Counting the cycles resulted in an accurate time scale and thus a sedimentation rate time series. Spectral analysis of the sedimentation rate time series shows that the short-term cycle of eccentricity (~125 k.y.) and the long term cycle of eccentricity (~400 k.y.) are pervasive throughout the Miocene record, together with the long-term ~2-m.y. eccentricity cycle. The Great Bahama Bank produced pulses of shallow carbonate input once every precessional (sea level) cycle during the Miocene and perhaps two pulses per cycle in the early Pliocene. The amount of sediment exported in these pulses appears to be controlled by eccentricity modulation of the precessional amplitude and therefore the amplitude of the sea-level rise. Finally, an increase in sedimentation rate just after the Miocene/Pliocene boundary is attributed to a change in the location and strength of sediment drift currents in the Florida Strait due to reorganization of the currents following the closure of the Panama Isthmus.

Ages, sedimentation rates and geochemical composition of ODP Site 162-983 sediments

A geochemical study of sediments from Ocean Drilling Program Site 983 was conducted to examine low-frequency variations in carbonate content as expressed by blue-band reflectance (450-500 nm) over the last 1.2 Ma. Sedimentary percent organic carbon, percent carbonate, and excess barium (Ba[ex]) were used as the primary tools to evaluate the factors responsible for these long-term changes. We observe positive correlation between the mass-accumulation rate of various biogenic components and the mass-accumulation rate of Ba(ex), especially in sediments younger than ~600 ka. Deeper in the section (~600-1200 ka), the correlation between Ba(ex) and the other biogenic tracers is weak. The lack of correlation between Ba(ex) and biogenic carbonate likely results either from a higher supply of terrigenous material at that time (which confounds Ba[ex] estimation), or remobilization of Ba resulting from low pore-water sulfate ion concentrations, or both. Nonbiogenic sediments at Site 983, represented by Th, K2O, and the molar Ti/Al ratio, exhibit cyclic variations that represent mixing between continental and oceanic (i.e., basaltic) terrigenous sources. The timing of these cycles matches that of the major glacial-interglacial cycles, which suggests that they result from the supply of continental material as ice-rafted debris during glacial periods and fine-grained basaltic material by bottom currents during interglacial periods. Given these observations, the most likely causes for the low-frequency carbonate variations observed in the Site 983 sediments are shifts in surface productivity and, to a lesser extent, dilution by the input of terrigenous material.