Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

Middle Miocene to Quaternary diatom biostratigraphy of DSDP Site 90-594

A diatom biostratigraphy is presented for middle Miocene through Quaternary sediments recovered from the Chatham Rise east of New Zealand's South Island. The upper 590 m of the 639.5-m composite-section Site 594 represents approximately 16 m.y. and is characterized by moderately to very poorly preserved diatoms of antarctic to temperate affinity. Pliocene through Quaternary assemblages are poorly preserved and dominated by antarctic-subantarctic species which provide detailed biostratigraphic control. Recognized are 11 of 14 zones of the middle upper Miocene to Quaternary Neogene Southern Ocean diatom zonation (NSD 7-NSD 20) of Ciesielski (1983; this chapter). Four Neogene Southern Ocean diatom zones (NSD 3-NSD 6) are recognized in the lower middle Miocene to middle upper Miocene of Site 594. Assemblages of this interval have a mixed high-latitude and temperate affinity; however, poor preservation limits correlation to high- and temperate-latitude zonal schemes. Neogene North Pacific diatom zones and subzones of NNPD 3 through NNPD 5 (Barron, in press, b) are correlated to Neogene Southern Ocean diatom zones NSD 3 through NSD 7: the upper portions of the Actinocyclus ingens Zone (NNPD 3) is correlative to the upper Nitzschia maleinterpretaria Zone (NSD 3); the Denticulopsis lauta Zone (NNPD 4) and Subzones a and b are correlative to the lower Coscinodiscus lewisianus Zone (NSD 4); and the D. hustedtü-D. lauta Zone (NNPD 5) and its Subzones a through d encompass the upper C. lewisianus Zone (NSD 4), N. grossepunctata Zone (NSD 5), N. denticuloides Zone (NSD 6), and the lower D. hustedtii-D. lauta Zone (NSD 7). A major disconformity spans the late Gilbert to early Gauss Chron (3.9-2.8 Ma). A second disconformity brackets the Miocene/Pliocene boundary; the section missing covers late Chron 5 and the early Gilbert chron (5.5-4.6 Ma). The remainder of the siliceous-fossil-bearing Miocene sediments at Site 594 appear to be correlative to lower paleomagnetic Chronozone 5 through upper Chronozone 16. Uppermost lower Miocene or lowermost middle Miocene sediments in the basal 50 m of Hole 594A are barren of diatoms.

Geochemistry and provenance of basaltic clasts within volcaniclastic debris flows at DSDP Site 89-585

Pebble-sized basaltic and glassy clasts were extracted from seamount-derived volcaniclastic debris flows and analyzed for various trace elements, including the rare earths, to determine their genetic relationships and provenance. All the clasts were originally derived from relatively shallow submarine lava flows prior to sedimentary reworking, and have undergone minor low-grade alteration. They are classified into three petrographic groups (A, B, and C) characterized by different phenocryst assemblages and variable abundances and ratios of incompatible elements. Group A (clast from Hole 585) is a hyaloclastite fragment which is olivine-normative and distinct from the other clasts, with incompatibleelement ratios characteristic of transitional or alkali basalts. Groups B and C (clasts from Hole 585A) are quartz-normative, variably plagioclase-clinopyroxene-olivine phyric tholeiites, all with essentially similar ratios of highly incompatible elements and patterns of enrichment in light rare earth elements (chrondrite-normalized). Variation within Groups B and C was governed by low-pressure fractionation of the observed phenocryst phases, whereas the most primitive compositions of each group may be related by variable partial melting of a common source. The clasts have intraplate chemical characteristics, although relative to oceanic hot-spot-related volcanics (e.g., Hawaiian tholeiites) they are marginally depleted in most incompatible elements. The source region was enriched in all incompatible elements, compared with a depleted mid-ocean-ridge basalt source.

(Table S3) Benthic foraminiferal Mg/Ca, Li/Ca and stable isotope ratios of ODP Site 122-761

The sensitivities of benthic foraminiferal Mg/Ca and Li/Ca to bottom water temperature and carbonate saturation state have recently been assessed. Here we present a new approach that uses paired Mg/Ca and Li/Ca records to calculate simultaneous changes in temperature and saturation state. Using previously published records, we first use this approach to document a cooling of deep ocean waters associated with the establishment of the Antarctic ice sheet at the Eocene-Oligocene climate transition. We then apply this approach to new records of the Middle Miocene Climate Transition from ODP Site 761 to estimate variations in bottom water temperature and the oxygen isotopic composition of seawater. We estimate that the oxygen isotopic composition of seawater varied by ~1 per mil between the deglacial extreme of the Miocene Climatic Optimum and the glacial maximum following the Middle Miocene Climate Transition, indicating large amplitude variations in ice volume. However, the longer-term change between 15.3 and 12.5 Ma is marked by a ~1°C cooling of deep waters, and an increase in the oxygen isotopic composition of seawater of ~0.6 per mil. We find that bottom water saturation state increased in the lead up to the Middle Miocene Climate Transition and decreased shortly after. This supports decreasing pCO2 as a driver for global cooling and ice sheet expansion, in agreement with existing boron isotope and leaf stomatal index CO2 records but in contrast to the published alkenone CO2 records.

Stable oxygen and carbon isotope record of foraminifera of ODP SIte 184-1146

Ocean Drilling Program Site 1146 was drilled within a small rift basin on the midcontinental slope of the northern South China Sea. It is located at 19°27.4'N, 116°16.37'E, in 2092 m water depth. This site was drilled to recover records of Asian monsoon variability into the middle Miocene with temporal resolution sufficient for orbital-scale analyses. Here we present oxygen and carbon isotopic measurements of planktonic foraminifers (Globigerinoides ruber) and benthic foraminifers (Uvigerina peregrina and Cibicides wuellerstorfi) as well as a preliminary age model for the top 185 meters composite depth (mcd).

Quaternary radiolarian counts from Site 181-1123

In the present work Quaternary radiolarian assemblages from the Southwest Pacific were investigated due to their importance for correlation and identification of climatic changes. The studied Ocean Drilling Program (ODP) Site 1123 (Leg 181) is situated on the northern flanks of the Chatham Rise, 1100 kilometres offshore eastern New Zealand and in a water depth o f 3290 metres. It is situated just north of the Subtropical Convergence (STC) in temperate climatic conditions, influenced by the cold deep Deep Western Boundary Current (DWBC) and by the subtropical East Cape Current (ECC) in shallow water depths. A continuous record of 79 sediment samples from this site with a temporal resolution of ~15,000 years provided a medium-resolution record of radiolarian assemblages through the Quaternary. This allowed investigations on how radiolarian assemblages are influenced by climatic variations at obliquity and eccentricity bandwidth, with periodic variations of 40,000, 100,000 and 400,000 years, respectively. Emphasis was given to changes in radiolarian assemblages through the Mid-Pleistocene climate transition (MPT) that marks a fundamental reorganisation in Earth's climate system by change from 40,000 to 100,000 year cycles. Glacial and interglacial variations in oceanography were investigated. Especially the influence of the DWBC was examined due to its input of deep and cold waters to the Pacific Ocean, which plays an important role in Earth's climate system. 167 radiolarian counting groups were examined concerning variations in radiolarian abundance, preservation, diversity, the relative abundance of orders, families, and selected species in order to detect influences of past climatic variations in the Southwest Pacific. No significant changes in radiolarian assemblages were found in coincidence with the onset of the MPT. Investigations led to the recognition of four characteristic phases within the last 1.2 million years. Within one of these phases (Phase Ill), about 160,000 years after the onset of the MPT, fundamental changes in radiolarian assemblages occurred. Investigations yielded highest diversity and highest numbers of nassellarians in abundant samples, whereas sparse samples were mostly poorly preserved and were dominated by spumellarians. Abundance of certain radiolarian families in interglacials or glacials indicated their usefulness as indicators for climatic conditions at Site 1123. Trends o f selected taxa within these families supported the significance of warm- or cool-water preference of these families. Use of 67 radiolarian species as climate indicators showed abundance of warm-water assemblages within interglacials, whereas abundance of cool-water species was increased within glacials. Depth distributional patterns of 52 radiolarian species indicated a strong influence of shallow waters, possibly the EEC, within interglacials and increased influence of deep and intermediate waters, possibly of southern-sourced character and the DWBC in glacial stages.

Age model and Plio-Pleistocene benthic stable oxygen isotope ratios of ODP Site 184-1143 in the Sourh China Sea

Based on benthic foraminiferal delta18O from ODP Site 1143, a 5-Myr astronomical timescale for the West Pacific Plio-Pleistocene was established using an automatic orbital tuning method. The tuned Brunhes/Matuyama paleomagnetic polarity reversal age agrees well with the previously published age of 0.78 Ma. The tuned ages for several planktonic foraminifer bio-events also agree well with published dates, and new ages for some other bio-events in the South China Sea were also estimated. The benthic delta18O from Site 1143 is highly coherent with the Earth's orbit (ETP) both at the obliquity and precession bands for the last 5 Myr, and at the eccentricity band for the last 2 Myr. In general, the 41-kyr cycle was dominant through the Plio-Pleistocene although the 23-kyr cycle was also very strong. The 100-kyr cycle became dominant only during the last 1 Myr. A comparison of the benthic delta18O between the Atlantic (ODP 659) and the East and West Pacific (846 and 1143) reveals that the Atlantic-Pacific benthic oxygen isotope difference ratio (Delta delta18OAtl-Pac) displays an increasing trend in three time intervals: 3.6-2.7 Ma, 2.7-2.1 Ma and 1.5-0.25 Ma. Each of the intervals begins with a rapid negative shift in Delta delta18OAtl-Pac, followed by a long period with an increasing trend, corresponding to the growth of the Northern Hemisphere ice sheet. This means that all three intervals of ice sheet growth in the Northern Hemisphere were accompanied at the beginning by a rapid relative warming of deep water in the Atlantic as compared to that of the Pacific, followed by its gradual relative cooling. This general trend, superimposed on the frequent fluctuations with glacial cycles, should yield insights into the processes leading to the boreal glaciation. Cross-spectral analyses of the Delta delta18OAtl-Pac with the Earth's orbit suggests that after the initiation of Northern Hemisphere glaciation at about 2.5 Ma, obliquity rather than precession had become the dominant force controlling the vertical structure or thermohaline circulation in the paleo-ocean.

Radiolarian biostratigraphy in sediments of ODP Site 202-1237

Site 1237 is located on Nazca Ridge ~140 km off the coast of Peru and thus within the offshore region of the Peru-Chile Current. A total of 83 samples were used to provide an initial radiolarian biostratigraphic framework for Site 1237; radiolarians are present to Sample 202-1237B-19H-2, 58-60 cm (186.45 meters composite depth [mcd]) and are of good to fair abundance and preservation. Site 1237 is influenced by both subtropical and northward-transported southern latitude waters, has 55 ash layers within the uppermost 166 m, and has minimal to gross reworking. Shipboard paleomagnetic results showed that the upper 200 m spanned the last 12 m.y., and in the upper 100 mcd, the paleomagnetic inclination pattern could be directly correlated to the geomagnetic polarity timescale (GPTS). Tropical biostratigraphy was used to establish the zonal boundaries for Site 1237, and the paleomagnetic and radiolarian stratigraphy were well correlated.

Age model for the time between 3.45 and 2.45 Ma of ODP Site 189-1172

Calcareous nannoplankton assemblages and benthic d18O isotopes of Pliocene deep-sea sediments of ODP site 1172 (East of Tasmania) have been studied to improve our knowledge of the Southern Ocean paleoceanography. Our study site is located just north of the Subtropical Front (STF), an ideal setting to monitor migrations of the STF during our study period, between 3.45 and 2.45 Ma. The assemblage identified at ODP site 1172 has been interpreted as characteristic for the transitional zone water mass, located south of the STF, based on: (i) the low abundances (< 1%) of subtropical taxa, (ii) relatively high percentages of Coccolithus pelagicus, a subpolar type species, (iii) abundances from 2-10% of Calcidiscus leptoporus, a species that frequently inhabits the zone south of the STF and (iv) the high abundances of small Noelaerhabdaceae which at present dominates the zone south of the STF. Across our interval the calcareous nannoplankton manifests glacial-interglacial variability. We have identified cold events, characterized by high abundances of C. pelagicus which coincide with glacial periods, except during G7. After 3.1 Ma cold events are more frequent, in concordance with global cooling trends. Around 2.75 Ma, the interglacial stage G7 is characterized by anomalous low temperatures which most likely are linked to definite closure of the Central American Seaway (CAS), an event that is believed to have had global consequences. A gradual increase of very small Reticulofenestra across our section marks a significant trend in the small Noelaerhabdaceae species group and has been linked to a general enhanced mixing of the water column in agreement with previous studies. It is suggested that a rapid decline of small Gephyrocapsa after isotopic stage G7 might be related to the cooling observed in our study site after the closure of the CAS.

Distribution of Cretaceous redeposited benthic foraminifers at DSDP Site 89-585

Cretaceous benthic foraminifers from Site 585 in the East Mariana Basin, western Pacific Ocean, provide an environmental and tectonic history of the Basin and the surrounding seamounts. Age diagnostic species (from a fauna of 155 benthic species identified) range from late Aptian to Maestrichtian in age. Displaced species in sediments derived from the tops and flanks of nearby seamounts were deposited sporadically on the Basin floor well below the carbonate compensation depth (CCD) at abyssal depths of 5000 to 6000 m. These depths, characterized by an indigenous assemblage of benthic foraminifers, recrystallized radiolarians, fish debris, and sponge spicules, existed in the Mariana Basin from late Aptian to the present. Early Albian and older edifice-building volcanism had reached the photic zone with associated shallow-water bank or reef environments. By middle Albian, the dominant source areas subsided to outer-neritic to upper-bathyal depths. Major volcanic activity ceased and fine-grained sediments were deposited by distal turbidites, although intermittent volcanism and the influx of rare neritic material continued until the late Albian. By the Cenomanian to Turonian, upper- to middle-bathyal depths were reached by the dominant source areas, and the sediments recovered from this interval include organic carbon-rich layers. Rare benthic foraminifers from the Coniacian-Santonian interval indicate a continuation of dominantly middle-bathyal source areas. A change in sedimentation during the Campanian-Maestrichtian from older zeolitic claystone to abundant chert in the Campanian, and nannofossil chalk and claystone in the Maestrichtian resulted from migration of the site beneath the equatorial productive zone due to northwestward plate motion. The appearance of rare middle-neritic and upper-bathyal species in the Maestrichtian interval associated with volcanogenic debris gives evidence of the remobilization and downslope transport of pelagic deposits due to thermally induced uplift. Episodic redeposition of shallow-water material during the Aptian-Albian was produced by edifice-building volcanism perhaps combined with eustatic lowering of sea level. The Cenomanian-Turonian pulse coincided with a low global sea-level stand as does the transported material during the Coniacian-Santonian. The Maestrichtian pulse was caused by renewed midplate volcanism that extended over a large area of the central Pacific.

Stable isotope record of benthic foraminifera from DSDP Site 68-502

Benthic foraminiferal delta13C data from site 502 in the Caribbean Sea (sill depth ?1800 m) indicate that throughout the past 2.6 m.y., glacial delta13C values in the middepth Atlantic were higher during glaciations than interglaciations. This is interpreted as indicating a greater proportion of Upper North Atlantic Deep Water (UNADW) relative to southern source waters during glaciations. The contribution of UNADW during interglaciations to the middepth Atlantic remained approximately constant, and the contribution during glaciations may have been as much as 10 % higher in the late Pleistocene than in the late Pliocene. This small increase is in striking contrast to the much larger decrease in glacial Lower North Atlantic Deep Water (LNADW) contribution relative to southern sources, from about 80% to about 20%, that occurred over the past 2.6 m.y. Glacial intensification over the past 2.6 m.y. was probably coupled with a decrease in northward heat transport by the upper limb of the North Atlantic circulation cell, as was previously suggested on the basis of a LNADW record alone. Late Pleistocene (1 Ma-present) delta13C values in the Caribbean Sea were approximately 0.2? higher than they were from 2.6 to 2.0 Ma. The delta13C rise is not due to an increase in the mean ocean delta13C value, nor can it be entirely attributed to an increase in the proportion of high-delta13C source waters. An increase in the delta13C value of the surface source waters must have contributed to the delta13C rise.