Geochemistry of terrigenous material in deep-sea sediments of the equatorial Pacific

Biological productivity in the modern equatorial Pacific Ocean, a region with high nutrients and low chlorophyll, is currently limited by the micronutrient Fe. In order to test whether Fe was limiting in the past and to identify potential pathways of Fe delivery that could drive Fe fertilization (i.e., dust delivery from eolian inputs vs. Fe supplied by the Equatorial Undercurrent), we chemically isolated the terrigenous material from sediment along a cross-equatorial transect in the central equatorial Pacific at 140°W and at Ocean Drilling Program Site 850 in the eastern equatorial Pacific. We quantified the contribution from each potential Fe-bearing terrigenous source using a suite of chemical- and isotopic discrimination strategies as well as multivariate statistical techniques. We find that the distribution of the terrigenous sources (i.e., Asian loess, South American ash, Papua New Guinea, and ocean island basalt) varies through time, latitude, and climate. Regardless of which method is used to determine accumulation rate, there also is no relationship between flux of any particular Fe source and climate. Moreover, there is no connection between a particular Fe source or pathway (eolian vs. Undercurrent) to total productivity during the Last Glacial Maximum, Pleistocene glacial episodes, and the Miocene "Biogenic Bloom". This would suggest an alternative process, such as an interoceanic reorganization of nutrient inventories, may be responsible for past changes in total export in the open ocean, rather than simply Fe supply from dust and/or Equatorial Undercurrent processes. Additionally, perhaps a change in Fe source or flux is related to a change in a particular component of the total productivity (e.g., the production of organic matter, calcium carbonate, or biogenic opal).

Glacial-interglacial record of ODP Site 181-1119 in the Canterbury Bright, Southwest Pacific Ocean

Ocean Drilling Program (ODP) Site 1119 is located at water depth 395 m near the subtropical front (STF; here represented by the Southland Front), just downslope from the shelf edge of eastern South Island, New Zealand. The upper 86.19 metres composite depth (mcd) of Site 1119 sediment was deposited at an average sedimentation rate of 34 cm/kyr during Marine Isotope Stages (MIS) 1-8 (0-252 ka), and is underlain across a ~25 kyr intra-MIS 8 unconformity by MIS 8.5-11 (277-367 ka) and older sediment deposited at ~14 cm/kyr. A time scale is assigned to Site 1119 using radiocarbon dates for the period back to ~39 ka, and, prior to then, by matching its climatic record with that of the Vostok ice core, which it closely resembles. Four palaeoceanographic proxy measures for surface water masses vary together with the sandy-muddy, glacial-interglacial (G/I) cyclicity at the site. Interglacial intervals are characterised by heavy delta13C, high colour reflectance (a proxy for carbonate content), low Q-ray (a proxy for clay content) and light delta18O; conversely, glacial intervals exhibit light delta13C, low reflectance, high Q-ray and heavy delta18O signatures. Early interglacial intervals are represented by silty clays with 10-105-cm-thick beds of sharp-based (Chondrites-burrowed), shelly, graded, fine sand. The sands are rich in foraminifera, and were deposited distant from the shoreline under the influence of longitudinal flow in relatively deep water. Glacial intervals comprise mostly micaceous silty clay, though with some thin (2-10 cm thick) sands present also at peak cold periods, and contain the cold-water scallop Zygochlamys delicatula. Interglacial sandy intervals are characterised by relatively low sedimentation rates of 5-32 cm/kyr; cold climate intervals MIS 10, 6 and 2 have successively higher sedimentation rates of 45, 69 and 140 cm/kyr. Counter-intuitively,and forced by the bathymetric control of a laterally-moving shoreline during G/I and I/G transitions, the 1119 core records a southeasterly (seaward) movement of the STF during early glacial periods, accompanied by the incursion of subtropical water (STW) above the site, and northwesterly (landward) movement during late glacial and interglacial times, resulting in a dominant influence then of subantarctic surface water (SAW). The history of passage of these different water masses at the site is clearly delineated by their characteristic delta13C values. The intervals of thin, graded sands-muds which occur within MIS 2-3, 6, 7.4 and 10 indicate the onset at times of peak cold of intermittent bottom currents caused by strengthened and expanded frontal flows along the STF, which at such times lay near Site 1119 in close proximity to seaward-encroaching subantarctic waters within the Bounty gyre. In common with other nearby Southern Hemisphere records, the cold period which represents the last glacial maximum lasted between ~23-18 ka at Site 1119, during which time the STF and Subantarctic Front (SAF) probably merged into a single intense frontal zone around the head of the adjacent Bounty Trough.

Benthic foraminifera across the Cretaceous/Paleogene boundary in ODP Hole 198-1210A

Deep-sea benthic foraminifera show important but transient assemblage changes at the Cretaceous/Paleogene (K/Pg) boundary, when many biota suffered severe extinction. We quantitatively analyzed benthic foraminiferal assemblages from lower bathyal-upper abyssal (1500-2000 m) northwest Pacific ODP Site 1210 (Shatsky Rise) and compared the results with published data on assemblages at lower bathyal (~ 1500 m) Pacific DSDP Site 465 (Hess Rise) to gain insight in paleoecological and paleoenvironmental changes at that time. At both sites, diversity and heterogeneity rapidly decreased across the K/Pg boundary, then recovered. Species assemblages at both sites show a similar pattern of turnover from the uppermost Maastrichtian into the lowermost Danian: 1) The relative abundance of buliminids (indicative of a generally high food supply) increases towards the uppermost Cretaceous, and peaks rapidly just above the K/Pg boundary, coeval with a peak in benthic foraminiferal accumulation rate (BFAR), a proxy for food supply. 2) A peak in relative abundance of Stensioeina beccariiformis, a cosmopolitan form generally more common at the middle than at the lower bathyal sites, occurs just above the buliminid peak. 3) The relative abundance of Nuttallides truempyi, a more oligotrophic form, decreases at the boundary, then increases above the peak in Stensioeina beccariiformis. The food supply to the deep sea in the Pacific Ocean thus apparently increased rather than decreased in the earliest Danian. The low benthic diversity during a time of high food supply indicates a stressed environment. This stress might have been caused by reorganization of the planktic ecosystem: primary producer niches vacated by the mass extinction of calcifying nannoplankton may have been rapidly (<10 kyr) filled by other, possibly opportunistic, primary producers, leading to delivery of another type of food, and/or irregular food delivery through a succession of opportunistic blooms. The deep-sea benthic foraminiferal data thus are in strong disagreement with the widely accepted hypothesis that the global deep-sea floor became severely food-depleted following the K/Pg extinction due to the mass extinction of primary producers ("Strangelove Ocean Model") or to the collapse of the biotic pump ("Living Ocean Model").

Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.

Age models and stable isotope analysis on sediment core Site 199-1218 from the equatorial Pacific

A 13-million-year continuous record of Oligocene climate from the equatorial Pacific reveals a pronounced "heartbeat" in the global carbon cycle and periodicity of glaciations. This heartbeat consists of 405,000-, 127,000-, and 96,000-year eccentricity cycles and 1.2-million-year obliquity cycles in periodically recurring glacial and carbon cycle events. That climate system response to intricate orbital variations suggests a fundamental interaction of the carbon cycle, solar forcing, and glacial events. Box modeling shows that the interaction of the carbon cycle and solar forcing modulates deep ocean acidity as well as the production and burial of global biomass. The pronounced 405,000-year eccentricity cycle is amplified by the long residence time of carbon in the oceans.

Benthic foraminifera extinctions in the Cenozoic record

In the late Pliocene-middle Pleistocene a group of 95 species of elongate, cylindrical, deep-sea (lower bathyal-abyssal) benthic foraminifera became extinct. This Extinction Group (Ext. Gp), belonging to three families (all the Stilostomellidae and Pleurostomellidae, some of the Nodosariidae), was a major component (20-70%) of deep-sea foraminiferal assemblages in the middle Cenozoic and subsequently declined in abundance and species richness before finally disappearing almost completely during the mid-Pleistocene Climatic Transition (MPT). So what caused these declines and extinction? In this study 127 Ext. Gp species are identified from eight Cenozoic bathyal and abyssal sequences in the North Atlantic and equatorial Pacific Oceans. Most species are long-ranging with 80% originating in the Eocene or earlier. The greatest abundance and diversity of the Ext. Gp was in the warm oceanic conditions of the middle Eocene-early Oligocene. The group was subjected to significant changes in the composition of the faunal dominants and slightly enhanced species turnover during and soon after the rapid Eocene-Oligocene cooling event. Declines in the relative abundance and flux of the Ext. Gp, together with enhanced species loss, occurred during middle-late Miocene cooling, particularly at abyssal sites. The overall number of Ext. Gp species present began declining earlier at mid abyssal depths (in middle Miocene) than at upper abyssal (in late Pliocene-early Pleistocene) and then lower bathyal depths (in MPT). By far the most significant Ext. Gp declines in abundance and species loss occurred during the more severe glacial stages of the late Pliocene-middle Pleistocene. Clearly, the decline and extinction of this group of deep-sea foraminifera was related to the function of their specialized apertures and the stepwise cooling of global climate and deep water. We infer that the apertural modifications may be related to the method of food collection or processing, and that the extinctions may have resulted from the decline or loss of their specific phytoplankton or prokaryote food source, that was more directly impacted than the foraminifera by the cooling temperatures.

Lead isotopes of feldspar in North Atlantic Ocean sediments

The provenance of ice-rafted debris (IRD) deposited in the North Atlantic before, during, and after Heinrich event 2 has been determined through measuring the lead isotopic composition of single feldspar grains and multiple-grain composites from the larger than 150-µm size fraction, from cores from the eastern and western North Atlantic and from the Labrador Sea. Single-grain analyses are used to identify the specific continental sources of the IRD, whereas composite samples are used to assess the relative IRD contributions from different sources. All single grains from Heinrich layer 2 (H 2) as well as H 2 composites plot along a correlation line on a 207Pb/204Pb versus 206Pb/204Pb diagram characteristic of the Churchill province of the Canadian shield. This is yet another strong piece of evidence that this Heinrich event was dominated by a massive iceberg discharge of the Laurentide ice sheet lobe located over Hudson Bay. In contrast, single grains from the ambient glacial sediment (above and below H 2) have multiple sources: many of them also lie along the correlation line with H 2 grains, but many others have Pb signatures consistent with derivation from the Grenville province and the Appalachian range in North America and possibly from Scandinavia and Greenland. Composites from the ambient sediment generally lie well to the right of the H 2 reference line in agreement with the results of the single-grain analyses. The evidence provided by lead isotopes regarding the dominant role played by the Hudson Bay lobe of the Laurentide ice sheet in the development of the Heinrich events lends support to the binge/purge model advanced by MacAyeal [1993a, b] that invokes trapping of geothermal heat by the base of the icecap and subsequent basal melting as the mechanism that triggered the Heinrich events.

Miocene magnetostratigraphy of ODP Site 199-1218 in the equatorial Pacific

Pliocene and Miocene magnetostratigraphy from ODP Site 1218 (Equatorial Pacific) has been obtained by measurements made on u-channel samples, augmented by about 50 discrete samples. U-channel samples were measured at 1 cm intervals and stepwise demagnetized in alternating fields up to a maximum peak field of 80 mT. The component magnetization directions were determined by principal component analysis for demagnetization steps in the 20-60 mT peak field range. A relatively small number of discrete samples were subject to both thermal and alternating field (AF) demagnetization and gave results compatible with u-channel measurements. Magnetostratigraphy from u-channel samples are compared with shipboard data that were based on blanket demagnetization at peak AF fields of 20 mT. U-channel measurements add more detail to the magnetostratigraphic record and allow identification of thin polarity zones especially in the upper part of the section were the sedimentation rates are very low (~2 m/Myr). The component magnetization directions determined from u-channel measurements also gave more reliable and precise estimates of inclination (paleolatitude). The magnetostratigraphy from Site 1218 can be unambiguously correlated with the reference geomagnetic polarity time scale and gives a means of dating the sedimentary sequence. Both Miocene-Pliocene and Oligocene-Miocene stage boundaries were easily identified from the magnetostratigraphic record. Although calculation of paleomagnetic poles is hindered by the low precision of the cores' azimuthal orientation, the data from both u-channel and discrete samples allow determination of the paleolatitude of the Site through time with good precision. Paleomagnetic data indicate that the paleolatitude of Site 1218 has increased form nearly equatorial latitude in the Oligocene to its present-day latitude close to 9°N. Within the precision of the paleomagnetic data, this is in agreement with current predictions of plate motion models based on fixed hotspots.

Os isotope ratios of Late Eocene sediments from the tropical Pacific

High resolution records (ca. 100 kyr) of Os isotope composition (187Os/188Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene 187Os/188Os excursion and confirm that the Late Eocene 187Os/ 188Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink (2003, doi:10.1016/S0012-821X(03)00137-7), is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene 187Os/188Os minimum can be placed at 34.5 +/- 0.1 Ma in the marine records. In addition, two other distinct features of the 187Os/188Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. +/-0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO2. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the 187Os/188Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; 187Os/188Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of 187Os/188Os records with high resolution benthic foraminiferal delta18O records across the Eocene-Oligocene transition suggests that 187Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater 187Os/188Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine 187Os/188Os records are obscured by recovery from the Late Eocene 187Os/188Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.

Radiocarbon ages and stable isotope measurements on sediment cores of the subarctic Pacific and its marginal seas

Under modern conditions only North Pacific Intermediate Water is formed in the northwest Pacific Ocean. This situation might have changed in the past. Recent studies with general circulation models indicate a switch to deep-water formation in the northwest Pacific during Heinrich Stadial 1 (17.5-15.0 ka) of the last glacial termination. Reconstructions of past ventilation changes based on paleoceanographic proxy records are still insufficient to test whether a deglacial mode of deep-water formation in the North Pacific Ocean existed. Here we present deglacial ventilation records based on radiocarbon-derived ventilation ages in combination with epibenthic stable carbon isotopes from the northwest Pacific including the Okhotsk Sea and Bering Sea, the two potential source regions for past North Pacific ventilation changes. Evidence for most rigorous ventilation of the intermediate-depth North Pacific occurred during Heinrich Stadial 1 and the Younger Dryas, simultaneous to significant reductions in Atlantic Meridional Overturning Circulation. Concurrent changes in d13C and ventilation ages point to the Okhotsk Sea as driver of millennial-scale changes in North Pacific Intermediate Water ventilation during the last deglaciation. Our records additionally indicate that changes in the d13C intermediate-water (700-1750 m water depth) signature and radiocarbon-derived ventilation ages are in antiphase to those of the deep North Pacific Ocean (>2100 m water depth) during the last glacial termination. Thus, intermediate- and deep-water masses of the northwest Pacific have a differing ventilation history during the last deglaciation.

Oligocene planktonic foraminifera from the Ontong Java Plateau

Ocean Drilling Program Hole 803D (Leg 130) from the western tropical Pacific (Ontong Java Plateau) and Hole 628A (Leg 101) from the western subtropical North Atlantic (Little Bahama Bank) contain rich assemblages of planktonic foraminifers. The uppermost Eocene-basal Miocene section of Hole 803D is apparently complete, whereas the Oligocene section of Hole 628A contains three unconformities based on planktonic foraminiferal evidence. Anomalous ranges are recorded for Chiloguembelina cubensis and Globigerinoides primordius. C. cubensis is found to range throughout the upper Oligocene of both sites, and G. primordius first occurs near the base of upper Oligocene Zone P22 in Hole 628A. Paleomagnetic stratigraphy provides constraints on the last occurrence (LO) of Subbotina angiporoides, the first occurrence (FO) of Globigerina angulisuturalis, the FO of Globigerinoides primordius, the FO of Paragloborotalia pseudokugleri, and the LO of Chiloguembelina cubensis. In general, taxon ranges, total diversity, and the composition of the planktonic foraminiferal assemblages from Holes 628A and 803D are similar. Differences in the composition of planktonic foraminiferal assemblages between the two sites are interpreted to be primarily the result of enhanced dissolution at Site 803 (e.g., paucity of Globigerina angulisuturalis and absence of G. ciperoensis). However, the greater abundances of Subbotina angiporoides in subtropical Hole 628A and Paragloborotalia opima in tropical Hole 803D are probably related to oceanographic differences between the two low-latitude sites. Comparison between the low and southern high latitudes illustrates some similarities in the composition of Oligocene planktonic foraminiferal assemblages as well as some important differences. Species such as Pseudohastigerina spp., Turborotalia increbescens, "Turborotalia" ampliapertura, Paragloborotalia opima, P. pseudokugleri, P. semivera/mayeri, Globigerinella obesa, Globigerina angulisuturalis, G. gortanii, G. ouachitaensis, G. sellii, G. tapuriensis, G. tripartita, G. pseudovenezuelana, Subbotina? eocaena and S.? yeguaensis are absent or have rare occurrences in the subantarctic Oligocene assemblages. Biogeographic gradients, although not as pronounced as during the late Neogene, were nonetheless significant during the Oligocene.

Hydrocarbon gar in sediments of the Costa Rica ubduction zone

At the active continental margin off Costa Rica substantial amounts of hydrocarbon gases are encountered in sediments. The molecular composition (C1-C3) of free hydrocarbon gas as well as the isotopic composition (d13C of methane and ethane and D of methane) was analysed on core samples (ranging between 50 and 380 m depth) collected at sites 1040-1043 which was drilled during ODP Leg 170. In addition, the molecular composition of the C1-C3 hydrocarbons and the d13C composition of C1 and C2 hydrocarbons was determined on adsorbed gas from selected depth intervals at Site 1041 (50-380 mbsf). The molecular composition, and stable carbon and hydrogen isotope signature of low molecular weight hydrocarbons from core sediments and gas pockets indicate that most of the gas was generated by microbial CO2-reduction. Beside d13C values of about -80 per mil for methane (which is typical for microbially- generated methane) extremely light d13C values of -55 per mil were measured for ethane. The carbon isotope composition of methane and ethane, as well as the C1/(C2+C3) ratio display distinct trends with increasing depth. Gas mixing calculations indicate that the percentage of thermally-generated ethane increases from 10% at about 75 mbsf to almost 80% at 380 mbsf. The fraction of thermogenic methane in this depth interval is calculated to range from 0.03 to 1.8% of the total methane. The small contribution of thermogenic methane would increase the d13C value by <1 per mil. Therefore, the increase of d13C of methane (by about 12 per mil) with depth cannot be explained by gas mixing alone. Instead, the observed d13C trend is caused by successive isotope depletion of the methane precursor within the sedimentary organic matter due to progressing microbial gas generation.