Strontium and boron geochemistry of ODP sites at Hydrate Ridge, eastern Pacific Ocean

ODP Leg 204, which drilled at Hydrate Ridge, provides unique insights into the fluid regime of an accretionary complex and delineates specific sub-seafloor pathways for fluid transport. Compaction and dewatering due to smectite-illite transition increase with distance from the toe of the accretionary prism and bring up fluids from deep within the accretionary complex to sampled depths (<= 600 mbsf). These fluids have a distinctly non-radiogenic strontium isotope signature indicating reaction with the oceanic basement. Boron isotopes are also consistent with a deep fluid source that has been modified by desorption of heavy boron as clay minerals change from smectite to illite. One of three major horizons serves as conduit for the transport of mainly fluid. Our results enable us to evaluate fluid migration pathways that play important roles on massive gas hydrate accumulations and seepage of methane-rich fluids on southern Hydrate Ridge.

Pliocene-Pleistocene stack of globally distributed benthic stable oxygen isotope records

We present a 5.3-Myr stack (the ''LR04'' stack) of benthic d18O records from 57 globally distributed sites aligned by an automated graphic correlation algorithm. This is the first benthic delta18O stack composed of more than three records to extend beyond 850 ka, and we use its improved signal quality to identify 24 new marine isotope stages in the early Pliocene. We also present a new LR04 age model for the Pliocene-Pleistocene derived from tuning the delta18O stack to a simple ice model based on 21 June insolation at 65 N. Stacked sedimentation rates provide additional age model constraints to prevent overtuning. Despite a conservative tuning strategy, the LR04 benthic stack exhibits significant coherency with insolation in the obliquity band throughout the entire 5.3 Myr and in the precession band for more than half of the record. The LR04 stack contains significantly more variance in benthic delta18O than previously published stacks of the late Pleistocene as the result of higher resolution records, a better alignment technique, and a greater percentage of records from the Atlantic. Finally, the relative phases of the stack's 41- and 23-kyr components suggest that the precession component of delta18O from 2.7-1.6 Ma is primarily a deep-water temperature signal and that the phase of d18O precession response changed suddenly at 1.6 Ma.

Age determination of Pacific Ocean sediments

Benthic and planktonic 14C ages are presented for the last glacial termination from marine sediment core VM21-30 from 617 m in the eastern equatorial Pacific. The benthic-planktonic 14C age differences in the core increased to more than 6000 years between Heinrich 1 time and the end of the Younger Dryas period. Several replicated 14C ages on different benthic and planktonic species from the same samples within the deglacial section of the core indicate a minimal amount of bioturbation. Scanning electron microscopy reveals no evidence of calcite alteration or contamination. The oxygen isotope stratigraphy of planktonic and benthic foraminifera does not indicate anomalously old (glacial age) values, and there is no evidence of a large negative stable carbon isotope excursion in benthic foraminifera that would indicate input of old carbon from dissociated methane. It appears, therefore, that the benthic 14C excursion in this core is not an artifact of diagenesis, bioturbation, or a pulse of methane. A benthic D14C stratigraphy reconstructed from the 14C ages from the deglacial section of VM21-30 appears to match that of Baja margin core MV99-MC19/GC31/PC08 (705 m), but the magnitude of the low-14C excursion is much larger in the VM21-30 record. This would seem to imply that the VM21-30 core was closer to the source of 14C-depleted waters during the deglaciation, but the source of this CO2 remains elusive.

Ages, biostratigraphic datums, and coiling ratios of Pulleniatina in sediments from DSDP Holes 15-154A and 16-157

Pliocene and Pleistocene planktonic foraminiferal biogeography and paleoceanography have been examined in Deep Sea Drilling Project (DSDP) sites of the Panama Basin (Pacific Ocean) and Colombian and Venezuelan Basins (Atlantic Ocean) to determine the timing of the isolation of Atlantic and Pacific tropical planktonic faunas resulting from the development of the Central American isthmus. Previous studies have suggested a late Miocene to middle Pliocene occurrence of this event. The Panama Basin (DSDP site 157) and the Colombian Basin (DSDP site 154A) share two early Pliocene biogeographic events: (1) great abundance of sinistral coiling Neogloboquadrina pachyderma at 4.3 m.y. ago at site 157 and 0.7 m.y. later at site 154A, and (2) a sinistral-to-dextral change in the coiling-direction preference in Pulleniatina 3.5 m.y. ago at both locations. Identification of these events farther to the east in the Venezuelan Basin (DSDP site 148) is complicated by insufficient lower Pliocene core recovery, but abundant sinistral N. pachydcrma appear to have extended far to the east in the Caribbean 3.6 m.y. ago; perhaps the early Pliocene abundance of this form is not indicative of cool water. The coiling-direction history and stratigraphic ranges of Pulleniatina became different in the Atlantic and Pacific Oceans during the early Pliocene; this is inferred to result from geographic isolation of the assemblages. Saito (1976) used the temporary disappearance of this genus from Atlantic waters at 3.5 m.y. ago to mark the closure of the Isthmus of Panama, but I show that in the Colombian Basin (site 154A) its disappearance was closer to 3.1 m.y. ago. This suggests the possibility of surface-water communication between the Atlantic and Pacific until that time.

Chemical composition and solubility of ocean phosphatized rocks in seawater

In order to elucidate possibility of limestone phosphatization during contact with seawater two sets of experiments were carried out: that of solubility of natural phosphates in seawater and that of deposition of phosphorus onto calcareous phase. Concentration of phosphorus in seawater used for solubility experiments varied from 39 to 338 µ/l, temperature was 5.5-17.5°C and pH 7.8-7.9. The lowest solubility was characteristic of ancient crystallized samples. The deposition experiments showed that in case when concentration of dissolved phosphate in seawater reaches 3 mg/l it might be sorbed on solid CaCO3 phase without forming its own mineral. The latter is able to form rapidly but only if magnesium is not present in solution. In magnesium-free water calcium phosphates precipitate when concentration of dissolved phosphorus is higher than 0.9-1.2 mg/l. These results show that phosphatization of limestones in marine environment takes place during their contact with pore water but not with marine bottom water.

Stable oxygen isotope ratios of benthic and planktonic foraminifera from early Miocene sediments of DSDP Site 90-593 on the Challenger Plateau, Pacific Ocean (Table 1)

Oxygen isotope data are compared with relative abundances of selected planktic foraminifera through a ca. 15 m interval at DSDP Site 593 (Tasman Sea, southwest Pacific, 40°S) in which there are prominent changes in population sizes, as well as several evolutionary events. We focus on the relation between faunal and climatic histories. The base of early Miocene oxygen isotope Zone Mi1b (uppermost planktic foraminiferal Zone N.6) is identified from closesampled (c. 14 kyr) isotope records of Globigerina woodi and Cibicides kullenbergi. Chronostratigraphic interpolations, using the first occurrences of Globorotalia praescitula, G. mimea and Praeorbulina curva give an age estimate of ca. 18.4 Ma (cf. 18.1 -18.3 Ma for the base of the zone at DSDP Site 608 (type level, north Atlantic, 43°N) ). Another significant benthic delta18O enrichment event, informally designated as the base of zone "Mi1c", is identified 10 m higher in the sequence at ca. 17.8 Ma. Populations of Globoquadriau dehiscens and Globigerinoides trilobus (inferred to be near the southern margin of their distributions) either reduced considerably or withdrew, particularly in the vicinity of zone "Mi1c". A bioseries linking Globorotalia incognita with G. zealandica developed following the benthic delta18O enrichment spike at the base of Zone Mi1b; the latter species became extinct (at least regionally) just above the base of zone "Mi1c". In contrast, the apparently opportunistic Globorotlia praescitula increased dramatically in abundance at this time; there were also transformations in its architecture, leading to the evolutionary appearance of G. miozea. While planktic foraminifera abundances often do not closely covary with the detailed isotope records and tend to be more stable through time, the near coincidence of evolutionary and biogeographic events with isotopic events suggests at least indirect adaptive responses to climatic changes. Early Miocene middle-latitude planktic foraminiferal evolution, biogeography, and biostratigraphy, may be intimately connected with climatic history.

Geochemistry and sedimentation rates of ODP Leg 199 sites and of surface sediments in the eastern Pacific ocean

We present the first high-resolution organic carbon mass accumulation rate (MAR) data set for the Eocene equatorial Pacific upwelling region, from Sites 1218 and 1219 of the Ocean Drilling Program. A maximum Corg MAR anomaly appears at 41 Ma and corresponds to a high carbonate accumulation event (CAE). Independent evidence suggests that this event (CAE-3) was a time of rapid cooling. Throughout the Eocene, organic carbon burial fluxes were an order of magnitude lower than fluxes recorded for the Holocene. In contrast, the expected organic carbon flux, calculated from the biogenic barium concentrations for these sites, is roughly equal to modern. A sedimentation anomaly appears at 41 Ma, when both the measured and the expected organic carbon MAR increases by a factor of two-three relative to the background Eocene fluxes. The rain of estimated Corg and barium from the euphotic zone to the sediments increased by factors of three and six, respectively. We suggest that the discrepancy between the expected and measured Corg in the sediments is a direct consequence of the increased metabolic rates of all organisms throughout the Eocene oceans and sediments. This hypothesis is supported by recent work in ecology and biochemical kinetics that recognizes the fundamental basis of ecology as following from the laws of thermodynamics. This dependence is now elucidated as the Universal Temperature Dependence (UTD) "law" of metabolism and can be applied to all organisms over their biologically relevant temperature range. The general pattern of organic carbon and barium deposition throughout the Eocene is consistent with the UTD theory. In particular, the anomaly at 41 Ma (CAE-3) is associated with rapid cooling, an event that triggered slower metabolic rates for all organisms, slower recycling of organic carbon in the water and sediment column, and, consequently, higher deposition of organic carbon in the sediments. This "metabolism-based" scenario is consistent with the sedimentation patterns we observe for both Sites 1218 and 1219.

10Be/9Be-based chronostratigraphy of ODP Hole 181-1121B from the Southwest Pacific Ocean

A 10Be/9Be-based chronostratigraphy has been determined for ODP 181, Site 1121 sediment core, recovered from the foot of the Campbell Plateau, Southwest Pacific Ocean. This core was drilled through the Campbell 'skin drift' in ca. 4500 m water depth on the mid-western margin of the extensive Campbell Nodule Field, beneath the flow of the major cold-water Deep Western Boundary Current (DWBC). In the absence of detailed biostratigraphy, beryllium isotopes have provided essential time information to allow palaeo-environmental interpretation to be undertaken on the upper 7 m of the core. Measured 10Be/9Be ratios of sediment, and of ferromanganese nodules entrapped in the sediment, decrease systematically with depth in the core, in accordance with radioactive decay. However, the 10Be/9Be data diverge from ca. 3 m below the seafloor (mbsf) to the top of the core, giving rise to several possible geochronological models. The preferred model assumes that the measured 10Be/9Be ratios of the nodule rims reflect initial 10Be/9Be ratios equivalent to contemporary seawater, and that these can be used to derive the true age of the sediment where the nodules occur. The nodule rim ages can be then used to interpret the sediment 10Be/9Be data, which indicate an overall age to ca. 7 mbsf of ca. 17.5 Ma. The derived chronology is consistent with diatom biostratigraphy, which indicates an age of 2.2-3.6 Ma at 1 mbsf. Calculated sedimentation rates range from 8 to 95 cm m.y.**-1, with an overall rate to 7 mbsf of ca. 39 cm m.y.**-1. The lowest rates generally coincide with the occurrence of entrapped nodules, and reflect periods of increased bottom current flow causing net sediment loss. Growth rates of individual nodules decrease towards the top of the sediment core, similar to the observed decrease in growth rate from core to rim of seafloor nodules from the Campbell Nodule Field. This may be related to an overall increase in the vigour of the DWBC from ca. 10 Ma to the present.

Illustration of manganese nodules and crust collected from the Suiko Seamount, Northwestern Pacific Ocean

An initial investigation has been undertaken on the chemical composition of the manganese nodules. The results of chemical analyses on each layer of single nodules reveal the periodic patterns of distribution for Mn, Fe, Cu, Pb, Zn, Ni and Co contents. The variations strongly suggest that those of the elements in nodules from this region are, at least, climatically controlled.

Illustration of manganese nodules and crust collected from the Suiko Seamount, Northwestern Pacific Ocean

Manganese nodules from the Suiko Seamount exhibit the significant characteristics in mineral compositions. Well crystallized todorokite and birnessite, which are principal manganese mineral phase in nodules, only occur in the oxide layer directly incasing pebbles and coarse sand. The preferential formation of todorokite or birnessite phases seem to be principally controlled by the reaction rate of iron-manganese oxides with trace elements such as Cu, Ni, Co, Zn, Pb concentrated in nodules, rather than redox characteristics of sedimentary environment or mineralogical diagenetic process.