Chemical and isotope composition of carbonate nodules and host bottom sediments from Core DM9-666, Gulf of California

Results of mineralogical and isotopic analyzes of sulfur and carbon in carbonate nodules and host bottom sediments and results of 14C measurement in carbonate nodules are reported. It is proved that the carbonate nodules formed 11-22 thousand years ago in anaerobic diagenesis of bottom sediments rich in organic matter. Isotopic light metabolic carbon dioxide was a source of carbonate for nodules. It formed during microbial degradation of organic matter of bottom sediments.

Stable carbon isotope ratios and the formation of dolomite in ODP Leg 175 sites

We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.

(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.

Planktic and benthic foraminifreral isotope data for ODP Site 207-1258

The mid-Cretaceous is widely considered the archetypal ice-free greenhouse interval in Earth history, with a thermal maximum around Cenomanian-Turonian boundary time (ca. 90 Ma). However, contemporaneous glaciations have been hypothesized based on sequence stratigraphic evidence for rapid sea-level oscillation and oxygen isotope excursions in records generated from carbonates of questionable preservation and/or of low resolution. We present new oxygen isotope records for the mid-Cenomanian Demerara Rise that are of much higher resolution than previously available, taken from both planktic and benthic foraminifers, and utilizing only extremely well preserved glassy foraminifers. Our records show no evidence of glaciation, calling into question the hypothesized ice sheets and rendering the origin of inferred rapid sea-level oscillations enigmatic. Simple mass-balance calculations demonstrate that this Cretaceous sea-level paradox is unlikely to be explained by hidden ice sheets existing below the limit of d18O detection.

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).

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.

Stable isotope record of Cretaceous samples of DSDP Hole 71-511

Oxygen isotope data for upper Turonian planktonic foraminifera at Deep Sea Drilling Project Site 511 (Falkland Plateau, 60°S paleolatitude) exhibit an ~2 per mil excursion to values as low as -4.66 per mil (Vienna Peedee belemnite standard; PDB) coincident with the warmest tropical temperature estimates yet obtained for the open ocean. The lowest planktonic foraminifer d18O values suggest that the upper ocean was as warm as 30-32°C. This is an extraordinary temperature for 60°S latitude but is consistent with temperatures estimated from apparently coeval mollusc d18O from nearby James Ross Island (65°S paleolatitude). Glassy textural preservation, a well-defined depth distribution in Site 511 planktonics, low sediment burial temperature (~32°C), and lack of evidence of highly depleted pore waters argue against diagenesis (even solid state diffusion) as the cause of the very depleted planktonic values. The lack of change in benthic foraminifer d18O suggests brackish water capping as the mechanism for the low planktonic d18O values. However, mixing ratio calculations show that the amount of freshwater required to produce a 2 per mil shift in ambient water would drive a 7 psu decrease in salinity. The abundance and diversity of planktonic foraminifera and nannofossils, high planktonic:benthic ratios, and the appearance of keeled foraminifera argue against lower-than-normal marine salinities. Isotope calculations and climate models indicate that we cannot call upon more depleted freshwater d18O to explain this record. Without more late Turonian data, especially from outside the South Atlantic basin, we can currently only speculate on possible causes of this paradoxical record from the core of the Cretaceous greenhouse.

Stable oxygen isotope record and lithogenic composition of ODP Hole 117-722B

The upper 38 m of Hole 722B sediments (Owen Ridge, northwest Arabian Sea) was sampled at 20 cm intervals and used to develop records of lithogenic percent, mass accumulation rate, and grain size spanning the past 1 m.y. Over this interval, the lithogenic component of Owen Ridge sediments can be used to infer variability in the strength of Arabian Sea summer monsoon winds (median grain size) and the aridity of surrounding dust source-areas (mass accumulation rate; MAR in g/cm**2/k.y). The lithogenic MAR has strong 100, 41, and 23 k.y. cyclicities and is forced primarily by changes in source-area aridity associated with glacial-interglacial cycles. The lithogenic grain size, on the other hand, exhibits higher frequency variability (23 k.y.) and is forced by the strength of summer monsoon winds which, in turn, are forced by the effective sensible heating of the Indian-Asian landmass and by the availability of latent heat from the Southern Hemisphere Indian Ocean. These forcing mechanisms combine to produce a wind-strength record which has no strong relationship to glacial-interglacial cycles. Discussion of the mechanisms responsible for production of primary Milankovitch cyclicities in lithogenic records from the Owen Ridge is presented elsewhere (Clemens and Prell, 1990, doi:10.1029/PA005i002p00109). Here we examine the 1 m.y. record from Hole 722B focusing on different aspects of the lithogenic components including an abrupt change in the monsoon wind-strength record at 500 k.y., core-to-core reproducibility, comparison with magnetic susceptibility, coherency with a wind-strength record from the Pacific Ocean, and combination frequencies in the wind-strength record. The Hole 722B lithogenic grain-size record shows an abrupt change at 500 k.y. possibly indicating decreased monsoon wind-strength over the interval from 500 k.y. to present. The grain-size decrease appears to be coincident with a loss of spectral power near the 41 k.y. periodicity. However, the grain-size decrease is not paralleled in the Globigerina bulloides upwelling record, an independent record of summer monsoon wind-strength (Prell, this volume). These observations leave us with competing hypotheses possibly involving: (1) a decrease in the sensitivity of monsoon windstrength to obliquity forcing, (2) decoupling of the grain size and G. bulloides records via a decoupling of the nutrient supply from wind-driven upwelling, and/or (3) a change in dust source-area or the patterns of dust transporting winds. Comparison of the lithogenic grain size and weight percent records from Hole 722B with those from a nearby core shows that the major and most minor events are well replicated. These close matches establish our confidence in the lithogenic extraction techniques and measurements. Further, reproducibility on a core-to-core scale indicates that the eolian depositional signal is regionally strong, coherent, and well preserved. The lithogenic weight percent and magnetic susceptibility are extremely well correlated in both the time and frequency domains. From this we infer that the magnetically susceptible component of Owen Ridge sediments is of terrestrial origin and transported to the Owen Ridge via summer monsoon winds. Because of the high correlation with the lithogenic percent record, the magnetic susceptibility record can be cast in terms of lithogenic MAR and used as a high resolution proxy for continental aridity. In addition to primary Milankovitch periodicities, the Hole 722B grain-size record exhibits periodicity at 52 k.y. and at 29 k.y. Both periodicities are also found in the grain-size record from piston core RC11-210 in the equatorial Pacific Ocean. Comparison of the two grain-size records shows significant coherence and zero phase relationships over both the 52 and 29 k.y. periodicities suggesting that the strengths of the Indian Ocean monsoon and the Pacific southeasterly trade winds share common forcing mechanisms. Two possible origins for the 52 and 29 k.y. periodicities in the Hole 722B wind-strength record are (1) direct Milankovitch forcing (54 and 29 k.y. components of obliquity) and (2) combination periodicities resulting from nonlinear interactions within the climate system. We find that the 52 and 29 k.y. periodicities show stronger coherency with crossproducts of eccentricity and obliquity (29 k.y.) and precession and obliquity (52 k.y.) than with direct obliquity forcing. Our working hypothesis attributes these periodicities to nonlinear interaction between external insolation forcing and internal climatic feedback mechanisms involving an interdependence of continental snow/ice-mass (albedo) and the hydrological cycle (latent heat availability).

Stable oxygen isotope record and relative abundances of planktonic foraminifera of ODP Hole 117-728A

High resolution stratigraphy based on oxygen isotope ratios of the planktonic foraminifers Neogloboquadrina dutertrei (d'Orbigny), Globigeriniodes ruber (d'Orbigny), and Globigerina bulloides (d'Orbigny), magnetic susceptibility, and calcium carbonate content covers the sedimentary record of ODP Hole 728A drilled on the Oman Margin from approximately 10 k.y. to 525 k.y., comprising isotopic stages 1-13. Below stage 13 isotopic stage boundaries cannot be defined with certainty in our data. Sediment accumulation rates were calculated from the isotopic record of N. dutertrei by matching it with the age model SPECMAP curve. During the glacial periods sediment accumulation rates were higher than during the interglacial periods, reflecting increased input from the shelf during low-stands of sea level and increased eolian input. Periodograms for the past 524 k.y. on oxygen isotope records of N. dutertrei, G. ruber, and G. bulloides, on calcium carbonate content, magnetic susceptibility, and on a foraminiferal fragmentation record show powers matching the Milankovitch periodicities. High powers are concentrated around 103 k.y. In the spectra of oxygen isotope ratios of N. dutertrei, magnetic susceptibility, and foraminiferal fragmentation these are significant at the 80% confidence level with respect to a first order autoregressive model. Power concentrations near 43 k.y., matching obliquity, are present but subdued in all spectra. Power concentrations near 23 k.y., matching precession, are significant in the spectra of the oxygen isotope record of N. dutertrei, magnetic susceptibility, and calcium carbonate content record. Fragmentation of planktonic foraminifers increased during the interglacial periods. This is attributed to dissolution of the tests in an expanded oxygen minimum zone (OMZ), where undersaturation of calcium carbonate is caused by enhanced production in the euphotic zone, which would suggest stronger monsoonal induced upwelling during interglacial periods. Extension of the OMZ could also be increased by outflow of low oxygen marginal basin bottom water.

Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.