C4-C7 alkenones in deep sea sediments

It is believed that C4 to C7 hydrocarbons in petroleum are formed by the cracking of organic matter at depths generally exceeding 1,000 m at temperatures in excess of 50 °C (Cordel, 1972; Dow, 1974; Tissot et al., 1974)). Also, none of the alkanes in the butane-heptane range are formed biologically as far as is known at present. Consequently, it is thought that they do not occur in shallow, Recent sediments. In 1962, I analysed 22 samples of Recent sediments from 7 different environments and verified that these hydrocarbons were not present at the p.p.m. level (Dunton and Hunt, 1962) although traces of a few hydrocarbons such as butane, isobutane, isopentane and n-heptane have been found (Sokolov, 1957; Veber and Turkeltaub, 1958; Erdman et al., 1958; Emery and Hoggan, 1958). No identification of individual hexanes or heptanes has been reported except when there has been clear evidence of seepage from deeper source sediments (McIver, 1973).

Late Eocene to Recent deep-sea benthic foraminifera from the Central equatorial Pacific Ocean

Benthic foraminifers were studied in upper Eocene to Recent core-catcher samples from DSDP Sites 573, 574, and 575. The sites are on a north-south transect from the equator to about 05°N at about 133°W, water depth 4300 to 4600 m. At Site 574 additional samples were used to study the Eocene/Oligocene boundary in detail. About 200 specimens were counted per sample. The fauna is highly diverse (about 50 to 70 species per sample) and is of low dominance. The diversity is not related to age or sub-bottom depth. Many species are cosmopolitan and probably have wide environmental tolerances. Fluctuations in frequency of some taxa (e.g., Nuttallides umbonifera, Epistominella exigua, and Uvigerina spp.) cannot be correlated from one site to another. Several common species (e.g. Oridorsalis umbonatus and Globocassidulina subglobosa) range from late Eocene to Recent. First and last appearances are generally difficult to define precisely because many species are rare. For some species these datums differ from one site to another, but several datum levels are within 1 m.y. at all sites. First and last appearances are most numerous in two intervals, the late Eocene to early Oligocene (about 32 to 37 Ma) and the early to middle Miocene (about 13 to 18.5 Ma). Isotopic events occur within each of these periods of benthic faunal change, but the isotopic events have a shorter duration and start after the initiation of the changes in the fauna. Changes in deep-sea benthic faunal composition are not directly related to short-term oceanographic changes as expressed in isotopic records.

Mineralogy, isotopic composition of oxygen, hydrogen and carbon, and oxygen isotopic temperature of deep-sea silica and coexisting carbonates (Table 1)

Water extracted from opal-CT ("porcellanite", "cristobalite"), granular microcrystalline quartz (chert), and pure fibrous quartz (chalcedony) in cherts from the JOIDES Deep Sea Drilling Project is 56? to 87? depleted in deuterium relative to the water in which the silica formed. This large fractionation is similar in magnitude and sign to that observed for hydroxyl in clay minerals and suggests that water extracted from these forms of silica has been derived from hydroxyl groups within the silica. Delta18O-values for opal-CT at sites 61, 64, 70B and 149 vary from 34.3? to 37.2? and show no direct correlation with depth of burial. Granular microcrystaUine quartz in these cores is 0.5 ? depleted in 18O relative to coexisting opal-CT at sediment depths of 100 m and the depletion increases to 2? for sediments buried below 384 m. These relationships suggest that opal-CT forms before significant burial while granular microcrystalline quartz forms during deeper burial at warmer temperatures. The temperature at which opal-CT forms is thus probably approximately equal to the temperature of the overlying bottom water. Isotopic temperatures deduced for opal-CT formation are preliminary and very approximate, but yield Eocene deep-water temperatures of 5-13°C, and 6°C for the upper Cretaceous sample. Pure euhedral quartz crystals lining a cavity in opal-CT at 388 m in core 8-70B-4-CC have a ~delta18O value of +29.8? and probably formed near maximum burial. The isotopic temperature is approximately 32 ° C.

(Table 1) Stable oxygen isotope ratios of benthic foraminifera from Pacific Ocean deep-sea sediments

The thermal structure of the Pacific Ocean between water depths of about 1 and 4.5 kilometers is estimated from the oxygen isotopic ratio of benthonic foraminifera from deep-drilled and piston cores of early Pliocene age (about 3 to 5 million years ago). The ratio of oxygen-18 to oxygen-16 in the early Pliocene at each site varies by an average of only ± 0.12 per mil (1 standard deviation). A plot of the oxygen isotopic ratio against modern bottom-water temperature is adequately fit by a line having a slope of - 0.26 per mil per degree Celsius (the equilibrium temperature dependence of calcite-water fractionation), suggesting that the temperature gradient of the Pacific Ocean during the early Pliocene was similar to that of today.

Calculated sea level records and deep ocean temperatures from DSDP and ODP sites

During the mid-Pleistocene transition the dominant 41 ka periodicity of glacial cycles transitioned to a quasi-100 ka periodicity for reasons not yet known. This study investigates the potential role of deep ocean hydrography by examining oxygen isotope ratios in benthic foraminifera. Oxygen isotope records from the Atlantic, Pacific and Indian Ocean basins are separated into their ice volume and local temperature/hydrography components using a piece-wise linear transfer function and a temperature calibration. Although our method has certain limitations, the deep ocean hydrography reconstructions show that glacial deep ocean temperatures approached freezing point as the mid-Pleistocene transition progressed. Further analysis suggests that water mass reorganisation could have been responsible for these temperature changes, leading to such stable conditions in the deep ocean that some obliquity cycles were skipped until precessional forcing triggered deglaciation, creating the apparent quasi-100 ka pattern. This study supports previous work that suggests multiples of obliquity cycles dominate the quasi-100 ka glacial cycles with precession components driving deglaciations.

Reevaluation of mid-Pliocene North Atlantic sea surface temperatures

Multiproxy temperature estimation requires careful attention to biological, chemical, physical, temporal, and calibration differences of each proxy and paleothermometry method. We evaluated mid-Pliocene sea surface temperature (SST) estimates from multiple proxies at Deep Sea Drilling Project Holes 552A, 609B, 607, and 606, transecting the North Atlantic Drift. SST estimates derived from faunal assemblages, foraminifer Mg/Ca, and alkenone unsaturation indices showed strong agreement at Holes 552A, 607, and 606 once differences in calibration, depth, and seasonality were addressed. Abundant extinct species and/or an unrecognized productivity signal in the faunal assemblage at Hole 609B resulted in exaggerated faunal-based SST estimates but did not affect alkenone-derived or Mg/Ca-derived estimates. Multiproxy mid-Pliocene North Atlantic SST estimates corroborate previous studies documenting high-latitude mid-Pliocene warmth and refine previous faunal-based estimates affected by environmental factors other than temperature. Multiproxy investigations will aid SST estimation in high-latitude areas sensitive to climate change and currently underrepresented in SST reconstructions. Copyright 2008 by the American Geophysical Union.

Evaluating the efficacy of planktonic foraminifer calcite and 18O data for sea surface temperature reconstruction for the Late Miocene

This study examines the efficacy of published δ18O data from the calcite of Late Miocene surface dwelling planktonic foraminifer shells, for sea surface temperature estimates for the pre-Quaternary. The data are from 33 Late Miocene (Messinian) marine sites from a modern latitudinal gradient of 64°N to 48°S. They give estimates of SSTs in the tropics/subtropics (to 30°N and S) that are mostly cooler than present. Possible causes of this temperature discrepancy are ecological factors (e.g. calcification of shells at levels below the ocean mixed layer), taphonomic effects (e.g. diagenesis or dissolution), inaccurate estimation of Late Miocene seawater oxygen isotope composition, or a real Late Miocene cool climate. The scale of apparent cooling in the tropics suggests that the SST signal of the foraminifer calcite has been reset, at least in part, by early diagenetic calcite with higher δ18O, formed in the foraminifer shells in cool sea bottom pore waters, probably coupled with the effects of calcite formed below the mixed layer during the life of the foraminifera. This hypothesis is supported by the markedly cooler SST estimates from low latitudes—in some cases more than 9 °C cooler than present—where the gradients of temperature and the δ18O composition of seawater between sea surface and sea bottom are most marked, and where ocean surface stratification is high. At higher latitudes, particularly N and S of 30°, the temperature signal is still cooler, though maximum temperature estimates overlap with modern SSTs N and S of 40°. Comparison of SST estimates for the Late Miocene from alkenone unsaturation analysis from the eastern tropical Atlantic at Ocean Drilling Program (ODP) Site 958—which suggest a warmer sea surface by 2–4 °C, with estimates from oxygen isotopes at Deep Sea Drilling Project (DSDP) Site 366 and ODP Site 959, indicating cooler than present SSTs, also suggest a significant impact on the δ18O signal. Nevertheless, much of the original SST variation is clearly preserved in the primary calcite formed in the mixed layer, and records secular and temporal oceanographic changes at the sea surface, such as movement of the Antarctic Polar Front in the Southern Ocean. Cooler SSTs in the tropics and sub-tropics are also consistent with the Late Miocene latitude reduction in the coral reef belt and with interrupted reef growth on the Queensland Plateau of eastern Australia, though it is not possible to quantify absolute SSTs with the existing oxygen isotope data. Reconstruction of an accurate global SST dataset for Neogene time-slices from the existing published DSDP/ODP isotope data, for use in general circulation models, may require a detailed re-assessment of taphonomy at many sites.