Sedimentation rates and isotope data of Pyrgo murrhina from DSDP Hole 14-141

Oxygen and carbon stable isotope data of Pyrgo murrhina and flux rates of calcium carbonate in the bio- and magnetostratigraphically dated sediment sequence at DSDP Site 141 were used for a reconstruction of the deep-water circulation in the Northeast Atlantic during Late Miocene and Pliocene times. A distinct change towards reduced advection of deep water recorded near 5.4 Ma is contemporaneous with the cessation of the outflow of the saline Mediterranean water into the Atlantic. During the Pliocene, between 4.5 and 2.75 Ma and between 2.1 and 1.8 Ma, North Atlantic Deep Water (NADW) circulation was sluggish and Site 141 possibly influenced by Antarctic Bottom Water (AABW). Near 2.75 Ma, the advection of well-oxidized NADW was strongly intensified. This change is related to an onset of major Arctic ice growth and/or a major cooling of NADW.

Mid-Pleistocene planktonic foraminiferal composition and IRD content in ODP Sites 162-980 and 162-984

We investigated surface and deep ocean variability in the subpolar North Atlantic from 1000 to 500 thousand years ago (ka) based on two Ocean Drilling Program (ODP) sites, Feni drift site 980 (55°29'N, 14°42'W) and Bjorn drift site 984 (61°25'N, 24°04'W). Benthic foraminiferal stable isotope data, planktic foraminiferal faunas, ice-rafted debris data, and faunally based sea-surface temperature estimates help test the hypothesis that oceanographic changes in the North Atlantic region were associated with the onset of the 100-kyr world during the mid-Pleistocene revolution. Based on percentage of Neogloboquadrina pachyderma (s) records from both sites, surface waters during interglacials and glacials were cooler in the mid-Pleistocene than during marine isotope stages (MIS) 5 and 6. In particular, interglaciations at Bjorn drift site 984 were significantly cooler. Faunal evidence suggests that the interglacial Arctic front shifted from a position between the two sites to a position northwest of Bjorn drift site 984 after ca. 610 ka. As during the late Pleistocene, we find faunal evidence for lagging surface warmth at most of the glacial initiations during the mid-Pleistocene. Each initiation is associated with high benthic d13C values that are maintained into the succeeding glaciation, which we term "lagging NADW production." These findings indicate that lagging warmth and lagging NADW production are robust features of the regional climate system that persist in the middle to late Pleistocene.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Methanol and ethanol analysis in marine sediment pore water

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

Quaternary carbonate record of ODP Hole 115-709A

The CaCO3 content in Quaternary deep-sea sediments from Pacific and Atlantic oceans have been suggested to respond differently to glacial/interglacial cycles; CaCO3 contents are highest during glacials in the Pacific but highest during interglacials in the Atlantic Ocean. It is not yet clear as to whether a Pacific or an Atlantic pattern of CaCO3 fluctuations dominates the Indian Ocean. We have analyzed the Ocean Drilling Program (ODP) Site 709A from the western equatorial Indian Ocean for the last 1370 ka to determine the relationships between percentages and fluxes of CaCO3 and Quaternary paleoclimatic changes. We also analyzed the coarse (>25 µm) and fine (<25 µm) fractions of CaCO3 in an attempt at estimating the influence of differences in productivity of foraminifera and calcareous nannofossils in shaping the CaCO3 record. Carbon isotopes and Ba/Al ratios were used as indices of productivity. Percentages and fluxes of CaCO3 in the total sediment and <25 µm fraction do not show any clear relationships to glacial/interglacial cycles derived from d18O of the planktonic foraminifera Globigerinoides ruber. This indicates that CaCO3 fluctuations at this site do not show either a Pacific or an Atlantic pattern of CaCO3 fluctuations. Fluxes of CaCO3 (0.38 to 2.46 g/cm**2/ ka) in total sediment and Ba/Al ratios (0.58 to 3.93 g/cm**2/ka) show six-fold variability through the last 1370 ka, which points out that productivity changes are significant at this site. Fluxes of the fine CaCO3 component demonstrate a 26-fold change (0.02 to 0.52 g/cm**2/ka), whereas the coarse CaCO3 component exhibit eight-fold change (0.13 to 1.07 g/cm**2/ka). This suggests that productivity variations of calcareous nannofossils are greater in comparison with the foraminifera. On the other hand, mean values of coarse CaCO3 fluxes are higher compared to those of fine CaCO3, which reveals that the foraminifera contribute more to the bulk CaCO3 flux than the calcareous nannofossils in the equatorial Indian Ocean.

Stable isotopic record of planktonic foraminifera of the Pacific Ocean

We determined the d18O and d13C of individual Globigerinoides ruber and Pulleniatina obliquiloculata from sediment traps located from 5°N to 12°S along 140°W in the Pacific Ocean to evaluate the effects of varying [CO3=] on shell d18O and d13C. Variations in the offset between shell d13C and d13CDIC (Dd13Cs-DIC) are attributed to differences in [CO3]2-, temperature, and shell size between sample sites. When Dd13Cs-DIC of G. ruber was corrected for variations in [CO3]2- using the experimental slope of Bijma et al. (1998), the residual Dd13Cs-DIC was correlated with mixed layer temperature (+0.10±0.04 per mil °C**-1). The slope of this temperature effect is consistent with experimental results. In P. obliquiloculata, Dd13Cs-DIC and temperature were strongly anticorrelated (?0.14±0.03 per mil C**-1). We are unable to separate the influences of [CO3]2- and temperature in this species without independent experimental data. Correcting for [CO3]2- variability on d18Os of G. ruber improves the accuracy of estimated sea surface temperatures.

Neogen carbonate and stable isotope record of ODP Hole 120-751A

Lower Miocene through upper Pleistocene benthic foraminifer assemblage records from Ocean Drilling Program Site 751 on the Southern Kerguelen Plateau (57°44'S, water depth 1634 m) were combined with benthic and planktonic foraminifer oxygen and carbon isotope records and high-resolution CaCO3 data from the same site. Implications for the Neogene productivity and paleoceanography of the southern Indian Ocean are discussed. We used distinctive features of the Miocene d18O and d13C curves for stratigraphic correlation. Coinciding with a lower middle Miocene hiatus from 14.2 to 13.4 Ma, there was a rapid increase in benthic d18O values by 1.2 per mil. This distinct increase occurs in middle Miocene benthic foraminifer oxygen isotope curves from all oceans. No major change, however, in benthic foraminifer faunal composition occurred in this period of growth of the Antarctic ice cap and cooling of deep ocean waters (14.9-14.2 Ma). A drastic change in benthic foraminifer faunas coincided with a hiatus from 8.4 to 5.9 Ma. Shortly after this hiatus, in the latest Miocene, the CaCO3 content of the sediments dropped from 75% to 0%. From that time ( 5.8 Ma) through the early Pliocene, Site 751 has been situated beneath a high biogenic siliceous productivity zone. Carbonate contents of upper Pliocene and Pleistocene sediments vary between 20% and 70%. The benthic foraminifer faunas in the uppermost Pliocene and lower Pleistocene reflect strong bottom current conditions, in contrast to those in the upper Pleistocene, which indicate calm sedimentation and high food supply. High d13C values of planktonic foraminifers compared with low values of benthic foraminifers suggest high primary productivity in the late Pleistocene. The changes in productivity were probably a result of latitudinal migration and meandering of the Polar Frontal Zone.

Age determination of sediment cores from the Weddell Sea

We report here the results of a study aimed at providing radiometric age control on glacial events in the Weddell Sea during the late Quaternary. Sediment cores from the eastern continental shelf, where the East Antarctic ice sheet was grounded, have recovered glacial-marine sediments resting on tills and the latter deposits predate the isotope stage 2 last glacial maximum. Sediment cores from the continental slope and rise sampled a prominent ice-rafted debris layer, and radiocarbon ages indicate that this ice-rafting event took place prior to 26 000 yr B.P. Thus, the combined data indicate that significant deglaciation of the Weddell Sea continental shelf took place prior to the last glacial maximum. Our data also suggest that the ice masses that border the Weddell Sea are more extensive than they were during the previous glacial minimum.

Strontium isotope data from DSDP Sites 32-305 and 62-463 and ODP Sites 113-689 and 113-690

Fluctuations in oxygen (d18O) and carbon (d13C) isotope values of benthic foraminiferal calcite from the tropical Pacific and Southern Oceans indicate rapid reversals in the dominant mode and direction of the thermohaline circulation during a 1 m.y. interval (71-70 Ma) in the Maastrichtian. At the onset of this change, benthic foraminiferal d18O values increased and were highest in low-latitude Pacific Ocean waters, whereas benthic and planktic foraminiferal d13C values decreased and benthic values were lowest in the Southern Ocean. Subsequently, benthic foraminiferal d18O values in the Indo-Pacific decreased, and benthic and planktic d13C values increased globally. These isotopic patterns suggest that cool intermediate-depth waters, derived from high-latitude regions, penetrated temporarily to the tropics. The low benthic d13C values at the Southern Ocean sites, however, suggest that these cool waters may have been derived from high northern rather than high southern latitudes. Correlation with eustatic sea-level curves suggests that sea-level change was the most likely mechanism to change the circulation and/or source(s) of intermediate-depth waters. We thus propose that oceanic circulation during the latest Cretaceous was vigorous and that competing sources of intermediate- and deep-water formation, linked to changes in climate and sea level, may have alternated in importance.