(Table T2) Sulfur isotopes of pore water from ODP Leg 201 sites

Fifty-seven interstitial water samples from six sites (Ocean Drilling Program Sites 1225-1229 and 1231) in the eastern equatorial Pacific Ocean and the Peru margin were analyzed for the stable sulfur isotopic composition (34S/32S) of dissolved sulfate along with major and minor ions. With the exception of Site 1231, sulfate from the interstitial fluids (d34S values as much as 89 per mil vs. the SF6-based Vienna-Canyon Diablo troilite standard) is found at depth to be enriched in 34S with respect to modern seawater sulfate (d34S = ~21 per mil), indicating that microbial sulfate reduction (MSR) took place to different extents at all investigated sites. Deeper sediments at Sites 1228 and 1229 are additionally influenced by diffusion of a sulfate-rich brine that has already undergone sulfate reduction. The intensity of MSR depends on the availability of substrate (organic matter), sedimentation conditions, and the active bacterial community structure. Formation of isotopically heavy diagenetic barite at the sulfate-methane transition zone is expected at Sites 1227 (one front), 1229 (two fronts), and probably Site 1228. At Site 1231, the constant sulfur isotopic composition of sulfate and concentrations of minor pore water ions indicate that suboxic (essentially iron and manganese oxide based) diagenesis dominates and no net MSR occurs.

Temperature and salinity reconstruction for the Last Interglacial Period in the North Atlantic Ocean

Eight deep-sea sediment cores from the North Atlantic Ocean ranging from 31° to 72°N are studied to reconstruct the meridional gradients in surface hydrographic conditions during the interval of minimum ice volume within the last interglacial period. Using benthic foraminiferal ?18O measurements and estimates of Sea Surface Temperature (SST) and Sea Surface Salinity (SSS), we show that summer SSTs and SSSs decreased gradually during the interval of minimum ice volume at high-latitude sites (52°-72°N) whereas they were stable or increased during the same time period at low-latitude sites (31°-41°N). This increase in meridional gradients of SSTs and SSSs may have been due to changes in the latitudinal distribution of summer and annual-average insolation and associated oceanic and atmospheric feedbacks. These trends documented for the Eemian ice volume minimum period are similar to corresponding changes observed during the Holocene and may have had a similar origin.

Age determination and geochemistry of corals from the North Pacific

A depth transect of deep-sea bamboo corals along the California margin provides evidence that coral strontium to calcium ratios (Sr/Ca[coral]) record seawater Sr/Ca ratios (Sr/Ca[sw]). A calibration was constructed utilizing Sr/Ca[coral] ratios and previously published Pacific Sr/Ca[sw] data (R**2 = 0.53, n = 12, p < 0.01): Sr/Ca[coral] (mmol/mol) = 4.62*Sr/Ca[sw] (mmol/mol) - 36.64. Sr/Ca[sw] is ultimately governed by the remineralization of Sr-containing shells of surface water-derived marine organisms (e.g., Acantharia) at intermediate water depths. California margin Sr/Cacoral records from 792 and 1295 m document fluctuations in Sr/Ca[sw] that appear decadal-scale. These results suggest that Sr/Casw may not be as stable as previously assumed and may be influenced by surface productivity on short timescales.

Major and rare earth element composition of ODP Site 191-1179 sediments, northwest Pacific

Depth profiles of major element and rare earth element (REE) abundances in sediment samples (mainly siliceous ooze and clay) recovered from Holes 1179B and 1179C at Site 1179, Ocean Drilling Program Leg 191 (41.4°N, 159.6°E) were determined. The oxidation states of Mn and Ce were determined by X-ray absorption near-edge structure. Some geochemical indicators were tested, including the MnO/TiO2 ratios, a bivariate diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), and other discrimination diagrams. The oxidation state of Mn is reduced Mn(II) in the depth profile below 0.60 meters below seafloor (mbsf), which is consistent with relatively low and high abundances of Mn in the sediments and pore waters, respectively. It is possible that the diagenetic effect on the oxidation state and abundance of Mn makes it difficult for the MnO/TiO2 ratio to reflect the depositional environment. The normalized ratio of La and Ce does not change very much with depth, suggesting that the diagenetic effect does not affect the REE signature in the sediments. On the diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), the sediments studied here plot at the boundary of the pelagic and continental margin fields. This suggests that continental material has contributed to the sediment to some degree, even though Site 1179 is in a pelagic region of the northwestern Pacific Ocean, >1600 km from Japan.

Paleomagnetic properties of igneous rocks from several DSDP and ODP sites, western Pacific

Oceanic basalts and other related igneous rocks are considered excellent recorders of the Earth's paleomagnetic field. Consequently, basalt core paleomagnetic data are valuable for the constraints they provide on plate tectonic motions, especially for oceanic plates such as the Pacific. Unfortunately, few Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) boreholes have been cored very deeply into the ocean crust. The result is that there are only a few sites at which a large enough number of basalt flows have been cored to properly average secular variation (e.g., Kono, 1980, doi:10.2973/dsdp.proc.55.135.1980; Cox and Gordon, 1984, doi:10.1029/RG022i001p00047). Furthermore, there are a number of sites where basaltic core samples were retrieved but the cores were not measured. Often this occurs because leg scientists had more important sections to work on, or the section was ignored because it was too short to record enough time to average secular variation and obtain a reliable paleolatitude. Even though it may not be possible to determine a precise paleolatitude from such short sections, measurements from a small number of flows are important because they can be combined with other coeval paleomagnetic data from the same plate to calculate a paleomagnetic pole (Gordon and Cox, 1980, doi:10.1111/j.1365-246X.1980.tb02642.x; Cox and Gordon, 1984, doi:10.1029/RG022i001p00047). For this reason, I obtained samples for paleomagnetic measurements from eight Pacific sites (169, 170, 171, 581, 597, 800, 803, and 865), most of which have not been previously measured for paleomagnetism.

Pliocene to Pleistocene planktonic foraminiferal datum levels in the North Pacific

Continuous late Neogene planktonic foraminiferal records have been studied in the deep-sea cores of DSDP Sites 173, 310, and 296 across mid-latitudes of the North Pacific. These three sites have been correlated on the basis of planktonic foraminiferal events and major paleoclimatic/paleoceanographic intervals and tied to diatom, radiolarian, and nannofossil datum levels, and paleomagnetic and isotopic stratigraphy. Ten planktonic foraminiferal datum levels have been recognized within these Pliocene to Pleistocene sections; two of these are recognizable within the Pleistocene and eight within the Pliocene. Six planktonic foraminiferal zones are proposed which combined with the foraminiferal datum levels provide a high resolution biostratigraphic correlation for the mid-latitudes of the North Pacific.

Oligocene magnetostratigraphy for equatorial Pacific ODP Sites

An Oligocene magnetostratigraphy from ODP Sites 1218 and 1219 (Equatorial Pacific) has been obtained by measurements made on u-channel samples, augmented by about 221 discrete samples. U-channel samples were measured at 1 cm intervals and were stepwise demagnetized in alternating fields (AF) up to a maximum peak field of 80 mT. The magnetization directions were determined at 1 cm intervals by principal component analysis of demagnetization steps in the 20 to 60 mT peak field range. A similar treatment was carried out on the discrete samples, which confirmed the results obtained with u-channel measurements. Sites 1218 and 1219 were precisely correlated based on multisensor track, paleontological and shipboard magnetostratigraphic data; this correlation is substantiated by u-channel measurements. Although the magnetostratigraphy obtained from the u-channels is similar to the interpretation deduced from shipboard measurements based on blanket demagnetization at peak AF of 20 mT, the u-channel results are substantially more robust since many interpretative uncertainties are resolved by the stepwise demagnetization and higher stratigraphic resolution. The temporal resolution of u-channel-based magnetic stratigraphy in the Oligocene section of Sites 1218 and 1219 is better than 5 kyr, and it is therefore suitable for detection of brief polarity subchrons. However, in spite of the high resolution, we did not find any reversals corresponding to the numerous cryptochrons identified in this time span by Cande and Kent (1995, doi:10.1029/94JB03098).

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.

Middle Eocene to early Oligocene planktonic and benthic foraminifers from ODP Hole 125-786A

Drilling at Site 786, located in the center of the Izu-Bonin forearc basin, penetrated an apparently continuous section of middle Eocene/lower Oligocene volcaniclastic breccias and nannofossil oozes. Planktonic foraminiferal faunas underwent a gradual transition from relatively high-diversity middle Eocene through late Eocene tropical or warm-water assemblages to a cooler-water, less diverse assemblage during the early Oligocene. In the cosmopolitan benthic foraminiferal faunas, the major transition occurred during the early late Eocene. Middle Eocene benthic assemblages resembling the bathyal 'Lenticulina' fauna (characterized by Osangularia mexicana, Cibicidoides eocaenus, and several buliminid species) changed to an upper Eocene abyssal 'Globocassidulina subglobosa' fauna (characterized by Cibicidoides praemundulus, Globocassidulina subglobosa, Gyroidinoides girardanus, Oridorsalis umbonatus, and Siphonodosaria aculeata). Even though no large, abrupt faunal changes appear to have been associated with the assumed Eocene/Oligocene boundary, benthic species turnover continued through the late Eocene and into the early Oligocene. This resulted in a slightly lower diversity early Oligocene fauna dominated by three species: Laevidentalina sp., Bulimina jarvisi, and Gyroidinoides girardanus. The progression from a middle Eocene bathyal 'Lenticulina' fauna, rather than an abyssal 'Nuttallides truempyi' fauna, to an abyssal 'Globocassidulina subglobosa' fauna during the early late Eocene, suggests that a bathymetric deepening occurred at Site 786. Increased water depths may have resulted from tectonic subsidence.

Age determination of the rhyolites of the Lord Howe Rise in the Southwest Pacific Ocean

Drilling at site 207 (DSDP Leg 21), located on the broad summit of the Lord Howe Rise, bottomed in rhyolitic rocks. Sanidine concentrates from four samples of the rhyolite were dated by the 40Ar/39Ar total fusion method and conventional K-Ar method, and yielded concordant ages of 93.7 +/- 1.1 my, equivalent to the early part of the Upper Cretaceous. At this time the Lord Howe Rise, which has continental-type structure, is thought to have been emergent and adjacent to the eastern margin of the Australian-antarctic continent. Subsequent to 94 my ago and prior to deposition of Maastrichtian (70-65 myBP) marine sediments on top of the rhyolitic basement of the Lord Howe Rise, rifting occurred and the formation of the Tasman Basin began by sea-floor spreading with rotation of the Rise away from the margin of Australia. Subsidence of the Rise continued until Early Eocene (about 50 myBP), probably marking the end of sea-floor spreading in the Tasman Basin. These large scale movements relate to the breakup of this part of Gondwanaland in the Upper Cretaceous.

Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.