3He/4He and 4He/20Ne ratios in pore water and gas in Pacific deep-sea sediments

We have measured the 3He/3He and 3He/20 Ne ratios of thirty-nine pore water and gas samples in deep-sea sediments collected at twelve sites on the Pacific Ocean bottom during the cruises of Deep Sea Drilling Project Legs 87, 89, 90 and 92. The 3He/4He and 4He/20Ne ratios vary from 0.000000215 to 0.00000165 and from 0.29 to 20, respectively. He in the sample is composed of four components: (1) atmospheric He dissolved in seawater; (2) atmospheric He with mantle-derived He in Pacific bottom water; (3) in situ radiogenic He in the sediment; and (4) crustal He in the basement rock. Assuming that the 20Ne contents are constant with the value of seawater, the depth variations in the 4He/20Ne ratios at five Sites, 583D, 594, 597A, 598A and 504B, may provide useful information on 4He flux at the ocean bottom. The estimated 4He fluxes vary from 2000 to 40000 atoms cm**-2 s**-1 and are one to three orders of magnitude less than those calculated from the excess He in deep ocean water. An overall similarity between the geographical distribution of the 3He/4He ratios and heat flow data is found in the study area, between the East Pacific Rise across the Pacific Ocean and the Japanese Islands. The tendency is well explained by a conventional sea-floor spreading model.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.

Eocene and Oligocene radiolarian biostratigraphy from the Southern Ocean

Eocene-Oligocene radiolarians from Ocean Drilling Program Sites 699, 702, and 703, Leg 114 of the Subantarctic Atlantic were examined in order to extend the tripartite zonation for the recovered cores based on results of similar analysis of Leg 120 submarine sediments from the Indian Ocean. Correlation of the two oceans is made by examining 23 biohorizons and the three zones, Eucyrtidium spinosum, Axoprunum irregularis, and Lychnocanoma conica, in ascending stratigraphic order. One new species, Eucyrtidium nishimurae, is described.

Ash layer characteristics and major element oxide content of glasses from ODP Sites 162-982 and 162-985

The Cenozoic volcanic activity on Iceland has been recorded in North Atlantic sediments drilled during several Ocean Drilling Program (ODP)/Deep Sea Drilling Project legs (Legs 104, 151, 152, 162, and 163). Leg 162 (North Atlantic-Arctic Gateways II) recovered ash layers at Sites 982, 985, and 907 (Jansen, Raymo, Blum, et al., 1996, doi:10.2973/odp.proc.ir.162.1996). The revisited Site 907 was first drilled during Leg 151, and the ash from this site has been described in detail by Lacasse et al. (1996, doi:10.2973/odp.proc.sr.151.122.1996) and Werner et al. (1996, doi:10.2973/odp.proc.sr.151.123.1996). Site 982 is located within the Hatton-Rockall Basin on the Rockall Plateau, which is situated west of the British Isles. Site 985 is located northeast of Iceland at the foot of the eastern slope of the Iceland Plateau, adjacent to the Norwegian Basin. Here we report chemical analyses of Neogene tephra layers from Holes 982A, 983B, 982C, 985A, and 985B. The sedimentary sequence at Site 982 spans the lower Miocene-Holocene; Site 985 recovered sediments spanning the upper Oligocene-Holocene. Twenty-two distinct ash layers and ash-bearing sediments were sampled in Holes 982A-982C (Cores 162-982A-16H through 24H, 162-982B-14H through 56X, and 162-982C-15H through 27H), and 59 ash layers were sampled in Holes 985A and 985B (Cores 162-985A-11H through 59X, and 162-985B-11H through 14H). Almost 50% of the sampled ash is strongly altered (predominantly from Site 985). A cluster of altered thin layers in the lower Pliocene of Site 985 (top of Unit III) is remarkable.

Organic carbon, age, lithology, and CPI-alkenes at DSDP Sites 57-440 and 56-436

"Bound" and "free" solvent-extractable lipids have been examined from Sections 440A-7-6, 440B-3-5, 440B-8-4, 440B-68-2, and 436-11-4. The compound classes studied include aliphatic and aromatic hydrocarbons, ketones, alcohols, and carboxylic acids. Carotenoids and humic acids have also been examined. The quantitative results are considered in terms of input indicators, diagenesis parameters, and structural classes. A difference in input is deduced across the Japan Trench, with a higher proportion of autochthonous components on the western inner trench slope compared with the more easterly, outer trench, wall and greater input in the early Pleistocene than in the Miocene. A variety of diagenetic transformations is observed at Site 440 as sample depth increases. Results are compared with those of samples from Atlantic Cretaceous sediments and from the Walvis Bay high productivity area.

Geochemistry of North Atlantic Igneous Province basalts

New Sr-Nd-Pb-Hf data require the existence of at least four mantle components in the genesis of basalts from the the North Atlantic Igneous Province (NAIP): (1) one (or more likely a small range of) enriched component(s) within the Iceland plume, (2) a depleted component within the Iceland plume (distinct from the shallow N-MORB source), (3) a depleted sheath surrounding the plume and (4) shallow N-MORB source mantle. These components have been available since the major phase of igneous activity associated with plume head impact during Paleogene times. In Hf-Nd isotope space, samples from Iceland, DSDP Leg 49 (Sites 407, 408 and 409), ODP Legs 152 and 163 (southeast Greenland margin), the Reykjanes Ridge, Kolbeinsey Ridge and DSDP Leg 38 (Site 348) define fields that are oblique to the main ocean island basalt array and extend toward a component with higher 176Hf/177Hf than the N-MORB source available prior to arrival of the plume, as indicated by the compositions of Cretaceous basalts from Goban Spur (~95 Ma). Aside from Goban Spur, only basalts from Hatton Bank on the oceanward side of the Rockall Plateau (DSDP Leg 81) lie consistently within the field of N-MORB, which indicates that the compositional influence of the plume did not reach this far south and east ~55 Ma ago. Thus, Hf-Nd isotope systematics are consistent with previous studies which indicate that shallow MORB-source mantle does not represent the depleted component within the Iceland plume (Thirlwall, J. Geol. Soc. London 152 (1995) 991-996; Hards et al., J. Geol. Soc. London 152 (1995) 1003-1009; Fitton et al., 1997 doi:10.1016/S0012-821X(97)00170-2). They also indicate that the depleted component is a long-lived and intrinsic feature of the Iceland plume, generated during an ancient melting event in which a mineral (such as garnet) with a high Lu/Hf was a residual phase. Collectively, these data suggest a model for the Iceland plume in which a heterogeneous core, derived from the lower mantle, consists of 'enriched' streaks or blobs dispersed in a more depleted matrix. A distinguishing feature of both the enriched and depleted components is high Nb/Y for a given Zr/Y (i.e. positive DeltaNb), but the enriched component has higher Sr and Pb isotope ratios, combined with lower epsilon-Nd and epsilon-Hf. This heterogeneous core is surrounded by a sheath of depleted material, similar to the depleted component of the Iceland plume in its epsilon-Nd and epsilon-Hf, but with lower 87Sr/86Sr, 208Pb/204Pb and negative DeltaNb; this material was probably entrained from near the 670 km discontinuity when the plume stalled at the boundary between the upper and lower mantle. The plume sheath displaced more normal MORB asthenosphere (distinguished by its lower epsilon-Hf for a given epsilon-Nd or Zr/Nb ratio), which existed in the North Atlantic prior to plume impact. Preliminary data on MORBs from near the Azores plume suggest that much of the North Atlantic may be 'polluted' not only by enriched plume material but also by depleted material similar to the Iceland plume sheath. If this hypothesis is correct, it may provide a general explanation for some of the compositional diversity and variations in inferred depth of melting (Klein and Langmuir, 1987 doi:10.1029/JB092iB08p08089) along the MAR in the North Atlantic.

The last occurrence of Proboscia curvirostris in the North Atlantic marine isotope stage 9-8

Well-preserved diatoms are present in high sedimentation rate Pleistocene cores retrieved on Ocean Drilling Program (ODP) Legs 151, 152, 162 and IMAGES cruises of R/V Marion Dufresne from the North Atlantic. Investigation of the stratigraphic occurrence of diatom species shows that the youngest diatom event observed in the area is the last occurrence (LO) of Proboscia curvirostris (Jousé) Jordan and Priddle. P. curvirostris is a robust species that can easily be identified in the sediments, and therefore can be a practical biostratigraphic tool. We have mapped its areal distribution, and found that it stretches from 40°N to 80°N in the North Atlantic. Further, we have correlated the LO P. curvirostris to the oxygen isotope records of six cores to refine the age of this biostratigraphic event. The extinction of P. curvirostris is latitudinally diachronous through Marine Isotope Stages (MIS) 9 to 8 within the North Atlantic. This is closely related to the paleoceanography of the area. P. curvirostris first disappeared within interglacial MIS 9 (324 ka) from the northern areas that are most sensitive to climatic forcing, like the East Greenland current and the sea-ice margin. It survived in mid-North Atlantic until the conditions of the MIS 8 (glaciation) became too severe (260 ka). In the North Pacific at ODP Site 883 the LO P. curvirostris falls within MIS 8. The observed overlap in age between the North Atlantic and the North Pacific strongly suggests that the extinction of P. curvirostris is synchronous between these oceans.

Strontium- and lead-isotope composition of some basalts at DSDP Hole 69-504B

Seventeen whole-rock samples, generally taken at 25- to 50-meter intervals from 5 to 560 meters sub-basement in Deep Sea Drilling Project Hole 504B, were analyzed for 87Sr/86Sr ratios, and rubidium and strontium concentrations. Ten of these samples also were analyzed for Pb-isotope composition. Strontium-isotope ratios for eight samples from the upper 260 meters of the hole range from 0.70287 to 0.70377, with a mean of 0.70320. In the interval 330 to 560 meters, five samples have a restricted range of 0.70259 to 0.70279, with a mean of 0.70266, almost identical to the average value of fresh mid-ocean-ridge basalts. In the interval 260 to 330 meters, approximately intermediate strontium- isotope ratios are found. The higher 87Sr/86Sr ratios in the upper part of the hole can be interpreted in terms of strontium-isotope alteration during basalt-sea-water interaction. Relative to average fresh mid-ocean ridge basalts, the upper 260 meters of basalts are enriched by an average of about 9% in sea-water strontium 87Sr/86Sr = 0.7091). This Sr presumably is located in the smectites, which, as the main secondary minerals throughout the hole, replace olivine and matrix glass and locally fill vesicles (analyzed samples contained no veins). The strontium-isotope data strongly suggest that the integrated flux of sea water through the upper part of the Hole 504B crust has been greater than through the lower part. This is also suggested by (1) the common occurrence of Feoxide- hydroxide minerals as alteration products above 270 meters, but their near absence below 320 meters, (2) the presence of vein calcite above 320 meters, but its near absence below this level, and (3) the occurrence of vein pyrite only below a depth of 270 meters. Sea-water circulation in the lower basalts may have been partly restricted by the greater number of relatively impermeable massive lava flows below 230 meters sub-basement. Although sufficient sea water was present within the lower part of the hole to produce smectitic alteration products, the overall water /rock ratio was low enough to prevent significant modification of strontium-isotope ratios. Lead-isotope ratios of Hole 504B basalts form approximately linear arrays in plots of 208Pb/204Pb and 207Pb/204Pb versus 206Pb/204Pb. The arrays are similar to those reported for basalts from other mid-ocean ridges. There is no trend in Hole 504B lead-isotope ratios with vertical position in the basement. The arrays indicate that the lead-isotope composition of the upper mantle from which the Hole 504B basaltic melts were derived was inhomogeneous.

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.