Pliocene and Pleistocene diatom datum levels of the Northwest Pacific

Thick sections of Pliocene and Pleistocene biosiliceous clay and ooze were recovered by the Hydraulic Piston Corer (I-IPC) at three northwest Pacific sites (DSDP Sites 578, 579, and 580). They contain a well-preserved paleomagnetic record which made it possible to evaluate diatom events used in low and high latitudes in the transitional region of the northwest Pacific. Equatorial Pacific events are usually isochronons between the equatorial and subarctic regions. However, species which have short ranges in low latitudes tend to have diachronous first and last appearances in higher latitudes. All subarctic North Pacific datum species are present in the sediments at three sites which lie north and south across the subarctic front, but their ranges become shorter in southern regions. They do not penetrate into the equatorial region. Spatial distributions of these events are influenced by the paleo-position of the subarctic front. The migration of species from their home-area outwards, in the form of the first appearance, is related to the fluctuations of the subarctic front. The last appearance of species is a response to the change of the surface water temperature that is beyond the limit of tolerance of the species, or an unstable oceanic environment due to major change of climate.

Trace element geochemistry of zircons frim in situ ocean lithoshere

We characterize the textural and geochemical features of ocean crustal zircon recovered from plagiogranite, evolved gabbro, and metamorphosed ultramafic host-rocks collected along present-day slow and ultraslow spreading mid-ocean ridges (MORs). The geochemistry of 267 zircon grains was measured by sensitive high-resolution ion microprobe-reverse geometry at the USGS-Stanford Ion Microprobe facility. Three types of zircon are recognized based on texture and geochemistry. Most ocean crustal zircons resemble young magmatic zircon from other crustal settings, occurring as pristine, colorless euhedral (Type 1) or subhedral to anhedral (Type 2) grains. In these grains, Hf and most trace elements vary systematically with Ti, typically becoming enriched with falling Ti-in-zircon temperature. Ti-in-zircon temperatures range from 1,040 to 660°C (corrected for a TiO2 ~ 0.7, a SiO2 ~ 1.0, pressure ~ 2 kbar); intra-sample variation is typically ~60-15°C. Decreasing Ti correlates with enrichment in Hf to ~2 wt%, while additional Hf-enrichment occurs at relatively constant temperature. Trends between Ti and U, Y, REE, and Eu/Eu* exhibit a similar inflection, which may denote the onset of eutectic crystallization; the inflection is well-defined by zircons from plagiogranite and implies solidus temperatures of ~680-740°C. A third type of zircon is defined as being porous and colored with chaotic CL zoning, and occurs in ~25% of rock samples studied. These features, along with high measured La, Cl, S, Ca, and Fe, and low (Sm/La)N ratios are suggestive of interaction with aqueous fluids. Non-porous, luminescent CL overgrowth rims on porous grains record uniform temperatures averaging 615 ± 26°C (2SD, n = 7), implying zircon formation below the wet-granite solidus and under water-saturated conditions. Zircon geochemistry reflects, in part, source region; elevated HREE coupled with low U concentrations allow effective discrimination of ~80% of zircon formed at modern MORs from zircon in continental crust. The geochemistry and textural observations reported here serve as an important database for comparison with detrital, xenocrystic, and metamorphosed mafic rock-hosted zircon populations to evaluate provenance.

Interstitial water chemistry at DSDP Leg 67 Holes

Interstitial water chemistry has proved to be a sensitive indicator for early diagenetic reactions, particularly those related to organic matter oxidation. Downhole chemical variations in the pore waters from Deep Sea Drilling Project Holes 496 and 497 on the Middle America Trench slope off Guatemala are anomalous because both salinity and chlorinity show strong decreases to half the values of seawater, and d18O values become positive (maximum of about +2.5% at the bottom of the holes). These observations are explained in terms of dilution of pore waters after retrieval as a result of decomposition of the gas hydrates before removal of pore waters by shipboard squeezing techniques. In all holes, except Hole 495 (drilled in pelagic sediments), decomposition of organic matter leads to rapid sulfate depletion and subsequent methane generation. Associated with methane generation are large increases in alkalinity and dissolved ammonia. The latter component causes ion exchange reactions with clay minerals, which results in maxima in magnesium and perhaps potassium. At greater depths, as yet unidentified reactions cause the removal of magnesium. Especially in the deeper Trench Sites 499 and 500, rapid variations in calcium, magnesium, and alkalinity occur in turbidite sequences.

Strontium-isotope stratigraphy and oxygen- and carbon-isotope record of Middle Jurassic to Early Cretaceous belemnites in the South Atlantic

87Sr/86Sr data of belemnites are presented from a Middle Jurassic-Early Cretaceous succession from the Falkland Plateau (Deep Sea Drilling Project Sites 511 and 330) that was deposited in a periodically anoxic, semi-enclosed shallow water basin. Diagenetically screened strontium-isotope values of 0.706789 rise to 0.707044 before increasing sharply to 0.707428 in the uppermost part of the sampled succession. Comparison with published strontium calibration curves suggests that the oldest samples were Callovian to Oxfordian in age, whilst the remainder of the Jurassic part of the succession consisted of Kimmeridgian and Early Tithonian age sediments. The nannofossil, dinoflagellate and molluscan assemblages provide comparable age determinations. The strontium-isotope analysis of the youngest belemnites points to a Hauterivian-Barremian age, whilst age interpretations based upon the fauna provide a wide age range from the Barremian to early Albian. Strontium-isotope stratigraphy of this succession hence offers increased age resolution providing data regarding the timing of episodes of bottom water anoxia which have been recorded throughout the South Atlantic Basin. Well-preserved belemnite specimens display an oxygen-isotope range between +0.08 and -2.22? (PDB, Peedee belemnite international standard) and a carbon-isotope range from +2.35 to -1.33? (PDB). Delta13C values become increasingly negative through the Late Jurassic-Early Cretaceous and in concert with the 87Sr/86Sr data reveal a trend that could be accounted for by increasing levels of weathering and erosion. The oxygen-isotope data if interpreted in terms of palaeotemperature are consistent with warm palaeotemperatures in the Kimmeridgian and slightly cooler temperatures for the Tithonian and Early Cretaceous parts of the succession. The proposed relative Kimmeridgian warmth (based upon strontium-isotope age assignments) is thus in good agreement with other published palaeotemperature records.

Stable isotope stratigraphy of ODP Site 167-1014

Late Quaternary oxygen (d18O) and carbon (d13C) isotopic records for the benthic foraminifer Uvigerina and the planktonic foraminifer Globigerina bulloides are presented for the upper 20 meters composite depth sediment sequence of Ocean Drilling Program Site 1014, Tanner Basin, in the outer California Borderland province. The benthic oxygen isotopic record documents a continuous >160-k.y. sequence from marine isotope Stage (MIS) 6 to the present day. The record closely resembles other late Quaternary North Pacific benthic isotope records, as well as the well-dated deep-sea sequence (SPECMAP), and thus provides a detailed chronologic framework. Site 1014 provides a useful record of the California response to climate change as it enters the southern California Border-land. Sedimentation rates are relatively constant and high (~11.5 cm/k.y. ). The planktonic foraminiferal record is well pre-served except during marine isotope Substages 5b and 5d, when normally high G. bulloides abundance is strongly diminished as a result of dissolution. The planktonic oxygen isotopic shift of ~3 per mil between the last glacial maximum and the Holocene suggests a surface water temperature shift of <7°C, similar to estimates from Hole 893A (Leg 146) to the north. Unlike Santa Barbara Basin, G. bulloides d18O values during the last interglacial (MIS 5) at Site 1014 were significantly higher than during the Holocene. In particular, marine isotope Substage 5e (Eemian) was ~0.8 per mil higher. This is unlikely to reflect a cooler Eemian but is instead the result of preferential dissolution of thin-shelled (low d18O) specimens during this interval. In this mid-depth basin, a large benthic d18O shift during Termination I suggests dramatic temperature and salinity changes in response to switches in the source of North Pacific Intermediate Water. Although d13C values of the planktonic foraminifer G. bulloides are in disequilibria with seawater and hence interpretations are limited, the G. bulloides record exhibits several negative d13C excursions found at other sites in the region (Sites 1017 and 893). This indicates a response of G. bulloides d13C to regional surface water processes along the southern California margin. A general increase in benthic carbon isotopic values (-1.75 per mil to -0.75 per mil) in Tanner Basin during the last 200 k.y. is overprinted with smaller fluctuations correlated with climate change. The coolest intervals during the last glacial maximum (MISs 2 and 4) exhibit lower benthic d13C values, which correlate with global 13C shifts. The opposite relationship is exhibited during the last interglacial before 85 ka, when lower benthic d13C values are associated with warmer intervals (marine isotope Substages 5c and 5e) of the last interglacial. These time intervals were also marked by decreased intermediate water ventilation. Increased dissolution and organic accumulation during Substages 5b and 5d are anticorrelated with the benthic d13C record. These results suggest that a delicate balance in intermediate water d13C has existed between the relative influences of global 13C and regional ventilation changes at the 1165-m water depth of Site 1014.

Planktic foraminiferal turnover across the Paleocene-Eocene transition in the Bay of Biscay, North Atlantic

Planktic foraminifera across the Paleocene-Eocene transition at DSDP Site 401 indicate that the benthic foraminiferal mass extinction occurred within Subzone P 6a of Berggren and Miller (1988), or PS of Berggren et al. (1995) and coincident with a sudden 2.0? excursion in 6r3C values. The benthic foraminiferal extinction event (BFEE) and Sr3C excursion was accompanied by a planktic foraminiferal turnover marked by an influx of warm water species (Morozovella and Acarinina), a decrease in cooler water species (Subbotina), a sudden short-term increase in low oxygen tolerant taxa (Chiloguembelina), and no significant species extinctions. These faunal changes suggest climatic warming, expansion of the oxygen minimum zone, and a well stratified ocean water column. Oxygen isotope data of the surface dweller M. subbotina suggest climate warming beginning with a gradual 0.5? decrease in delta180 in the 175 cm preceding the benthic foraminiferal extinction event followed by a sudden decrease of 1? (4°C) at the BFEE. The delta13C excursion occurred over 27 cm of sediment and, assuming constant sediment accumulation rates, represents a maximum of 23 ka. Recovery to pre-excursion delta13C values occurs within 172 cm, or about 144 ka. Climate cooling begins in Subzone P 6c as indicated by an increase in cooler water subbotinids and acarininids with rounded chambers and a decrease in warm water morozovellids.

Over-determined charbonate chemstry dataset from different kinds of manipulation (TA, DIC) and water types (natural and artificial seawater)

The growing field of ocean acidification research is concerned with the investigation of organism responses to increasing pCO2 values. One important approach in this context is culture work using seawater with adjusted CO2 levels. As aqueous pCO2 is difficult to measure directly in small-scale experiments, it is generally calculated from two other measured parameters of the carbonate system (often AT, CT or pH). Unfortunately, the overall uncertainties of measured and subsequently calculated values are often unknown. Especially under high pCO2, this can become a severe problem with respect to the interpretation of physiological and ecological data. In the few datasets from ocean acidification research where all three of these parameters were measured, pCO2 values calculated from AT and CT are typically about 30% lower (i.e. ~300 µatm at a target pCO2 of 1000 µatm) than those calculated from AT and pH or CT and pH. This study presents and discusses these discrepancies as well as likely consequences for the ocean acidification community. Until this problem is solved, one has to consider that calculated parameters of the carbonate system (e.g. pCO2, calcite saturation state) may not be comparable between studies, and that this may have important implications for the interpretation of CO2 perturbation experiments.

Calcareous nannofossils of ODP Hole 177-1090D

Calcareous nannofossil assemblages have been investigated at Ocean Drilling Program (ODP) Site 1090 located in the modern Subantarctic Zone, through the Pleistocene Marine Isotope Stages (MIS) 34-29, between 1150 and 1000 ka. A previously developed age model and new biostratigraphic constraints provide a reliable chronological framework for the studied section and allow correlation with other records. Two relevant biostratigraphic events have been identified: the First Common Occurrence of Reticulofenestra asanoi, distinctly correlated to MIS 31-32; the re-entry of medium Gephyrocapsa at MIS 29, unexpectedly similar to what was observed at low latitude sites. The composition of the calcareous nannofossil assemblage permits identification of three intervals (I-III). Intervals I and III, correlated to MIS 34-32 and MIS 30-29 respectively, are identified as characteristic of water masses located south of the Subtropical Front and reflecting the southern border of Subantarctic Zone, at the transition with the Polar Front Zone. This evidence is consistent with the hypothesis of a northward shift of the frontal system in the early Pleistocene with respect to the present position and therefore a northernmost location of the Subantarctic Front. During interval II, which is correlated to MIS 31, calcareous nannofossil assemblages display the most significant change, characterized by a distinct increase of Syracosphaera spp. and Helicosphaera carteri, lasting about 20 ky. An integrated analysis of calcareous nannofossil abundances and few mineralogical proxies suggests that during interval II, Site 1090 experienced the influence of subtropical waters, possibly related to a southward migration of the Subtropical Front, coupled with an expansion of the warmer Agulhas Current at the core location. This pronounced warming event is associated to a minimum in the austral summer insolation. The present results provide a broader framework on the Mid-Pleistocene dynamic of the ocean frontal system in the Atlantic sector of the Southern Ocean, as well as additional evidence on the variability of the Indian-Atlantic ocean exchange.

(Table 1) Sea-surface temperatures, intermediate-water temperatures, and latitudinal gradient at three time slices at the end of the Cretaceous

Climatic and oceanographic variations during the last 2 m.y. of the Maastrichtian inferred from high-resolution (10 k.y.) stable isotope analysis of the mid-latitude South Atlantic Deep Sea Drilling Project Site 525 reveal a major warm pulse followed by rapid cooling prior to the Cretaceous-Tertiary boundary. Between 66.85 and 65.52 Ma, cool but fluctuating temperatures average 9.9 and 15.4°C in intermediate and surface waters, respectively. This interval is followed by an abrupt short-term warming between 65.45 and 65.11 Ma, which increased temperatures by 2-3°C in intermediate waters, and decreased the vertical thermal gradient to an average of 2.7°C. This warm pulse may be linked to increased atmospheric pCO2, increased poleward heat transport, and the switch of an intermediate water source from high to low-middle latitudes. During the last 100 k.y. of the Maastrichtian, intermediate and surface temperatures decreased by an average of 2.1 and 1.4°C, respectively, compared to the maximum temperature between 65.32 and 65.24 Ma.

Nd-Sr isotopic composition of foraminifera and bulk sediments

We present new isotopic data for sedimentary planktonic foraminifera, as well as for potential water column and sedimentary sources of neodymium (Nd), which confirm that the isotopic composition of the foraminifera is the same as surface seawater and very different from deep water and sedimentary Nd. The faithfulness with which sedimentary foraminifera record the isotopic signature of surface seawater Nd is difficult to explain given their variable and high Nd/Ca ratios, ratios that are often sedimentary foraminifera, ratios that are often much higher than is plausible for direct incorporation within the calcite structure. We present further data that demonstrate a similarly large range in Nd/Ca ratios in plankton tow foraminifera, a range that may be controlled by redox conditions in the water column. Cleaning experiments reveal, in common with earlier work, that large amounts of Nd are released by cleaning with both hydrazine and diethylene triamine penta-acetic acid, but that the Nd released at each step is of surface origin. While further detailed studies are required to verify the exact location of the surface isotopic signature and the key controls on foraminiferal Nd isotope systematics, these new data place the use of planktonic foraminifera as recorders of surface water Nd isotope ratios, and thus of variations in the past supply of Nd to the oceans from the continents via weathering and erosion, on a reasonably sure footing.

Pliocene/Pleistocene benthic foraminiferal abundances from six drilling cores

Twenty percent (19 genera, 95 species) of cosmopolitan, deep-sea (500-4000 m), benthic foraminiferal species became extinct during the late Pliocene-Middle Pleistocene (3-0.12 Ma), with the peak of extinctions (76 species) occurring during the mid-Pleistocene Climate Transition (MPT, 1.2-0.55 Ma). One whole family (Stilostomellidae, 30 species) was wiped out, and a second (Pleurostomellidae, 29 species) was decimated with just one species possibly surviving through to the present. Our studies at 21 deep-sea core sites show widespread pulsed declines in abundance and diversity of the extinction group species during more extreme glacials, with partial interglacial recoveries. These declines started in the late Pliocene in southern sourced deep water masses (Antarctic Bottom Water, Circumpolar Deep Water) and extending into intermediate waters (Antarctic Intermediate Water, North Atlantic Deep Water) in the MPT, with the youngest declines in sites farthest downstream from high-latitude source areas for intermediate waters. We infer that the unusual apertural types that were targeted by this extinction period were adaptations for a specific kind of food source and that it was probably the demise of this microbial food that resulted in the foraminiferal extinctions. We hypothesize that it may have been increased cold and oxygenation of the southern sourced deep water masses that impacted on this deep water microbial food source during major late Pliocene and Early Pleistocene glacials when Antarctic ice was substantially expanded. The food source in intermediate water was not impacted until major glacials in the MPT when there were significant expansion of polar sea ice in both hemispheres and major changes in the source areas, temperature, and oxygenation of global intermediate waters.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Siliceous microfossil assemblage and accumulation rate variations across the Middle Eocene Climatic Optimum at ODP Site 171-1051

The Middle Eocene Climatic Optimum (MECO; ~ 40 million years ago [Ma]) is one of the most prominent transient global warming events in the Paleogene. Although the event is well documented in geochemical and isotopic proxy records at many locations, the marine biotic response to the MECO remains poorly constrained. We present new high-resolution, quantitative records of siliceous microplankton assemblages from the MECO interval of Ocean Drilling Program (ODP) Site 1051 in the subtropical western North Atlantic Ocean, which are interpreted in the context of published foraminiferal and bulk carbonate stable isotope (d18O and d13C) records. High diatom, radiolarian and silicoflagellate accumulation rates between 40.5 and 40.0 Ma are interpreted to reflect an ~ 500 thousand year (kyr) interval of increased nutrient supply and resultant surface-water eutrophication that was associated with elevated sea-surface temperatures during the prolonged onset of the MECO. Relatively low pelagic siliceous phytoplankton sedimentation accompanied the peak MECO warming interval and the termination of the MECO during an ~ 70 kyr interval centered at ~ 40.0 Ma. Following the termination of the MECO, an ~ 200-kyr episode of increased siliceous plankton abundance indicates enhanced nutrient levels between ~ 39.9 and 39.7 Ma. Throughout the Site 1051 record, abundance and accumulation rate fluctuations in neritic diatom taxa are similar to the trends observed in pelagic taxa, implying either similar controls on diatom production in the neritic and pelagic zones of the western North Atlantic or fluctuations in sea level and/or shelf accommodation on the North American continental margin to the west of Site 1051. These results, combined with published records based on multiple proxies, indicate a geographically diverse pattern of surface ocean primary production changes across the MECO. Notably, however, increased biosiliceous accumulation is recorded at both ODP Sites 1051 and 748 (Southern Ocean) in response to MECO warming. This may suggest that increased biosiliceous sediment accumulation, if indeed a widespread phenomenon, resulted from higher continental silicate weathering rates and an increase in silicic acid supply to the oceans over several 100 kyr during the MECO.