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.

Paleoclimatate of the Middle Burdigalian-Langhian period in Turkey

The Miocene is the last warm episode in Earth history, and this episode was well recorded in Turkey as shown by plant distribution and inferred numerical temperature values. In this study, Ören-Kultak, Hüssamlar and Karacaagac palynofloras from western Turkey, which are characterized by the thermophilous plants (Engelhardia, Sapotaceae, Cyrillaceae, Avicennia, Arecaceae, Palmae), are described. Age determinations of these palynofloras (middle Burdigalian-Langhian) are strengthened by the mammalian fossil record (MN4-5) and strontium isotope results. Palaeoclimate is humid and warm subtropical during the middle Burdigalian-Langhian time interval in Europe and Turkey. However, temperature difference has been observed between Europe and Turkey during this time interval and it could be explained by the palaeogeographic position of countries. Despite some discrepancies in the climatic values and palaeovegetation groups, warm climatic conditions are recorded, based on the palynofloras, in Turkey (Cayyrhan, Havza, Can, Etili, Gönen, Bigadic, Emet, Kirka and Kestelek, Sabuncubeli, Soma, Tire, Kulogullary, Bascayyr, Hüssamlar and Karacaagac), Greece and elsewhere in Europe throughout the middle Burdigalian-Langhian period. This warming is related to the Middle Miocene Climatic Optimum period. Carbon and oxygen isotope values obtained from tooth enamel of Gomphotherium sp. from Kultak and Hüssamlar indicate similar ecological condition during the Burdigalian-Langhian time. This isotopic result and high MAPDRY value from the Kultak locality are in agreement with ecological interpretation of mammalian fossils. Besides, according to the precipitation values, central and northwestern Anatolian sites provide more rainfall during the Burdigalian-Langhian time interval than the western Anatolian sites.

(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.

Occurrence and stratigraphy of Coccolithus pelagicus in ODP Hole 120-747A

A record based on counts of the relative abundance of the dominant calcareous nannofossil taxa Coccolithus pelagicus and Reticulofenestra spp. in sediments recovered from Ocean Drilling Program Hole 747A (Kerguelen Plateau, Southern Indian Ocean) is established in this paper. This record (17 m.y. long) virtually spans the entire Miocene. Broad, steplike variations in the abundance of C. pelagicus range between 0% and 96%. Based on these variations, five stratigraphic units characterized by high abundance in C. pelagicus are delineated. We suggest that these variations are caused by water-mass movements (such as the north/south shifting of a front). This pronounced signal is compared with paleoceanographic events revealed by isotopic (d18O and d13C) studies. The five defined units are tentatively correlated to well-known global isotopic events. In particular, Units A and D correlate respectively with the Oligocene/Miocene boundary glaciation and the middle Miocene cooling event. Time-series analysis indicates the presence of the three main periodic components of the eccentricity of the Earth's orbit. A 200-k.y. cycle is also present. The stratigraphic and paleoceanographic significance of this record is discussed.

Geochemistry and morphometry on planktonic foraminifera

About one third of the anthropogenic carbon dioxide (CO2) released into the atmosphere in the past two centuries has been taken up by the ocean. As CO2 invades the surface ocean, carbonate ion concentrations and pH are lowered. Laboratory studies indicate that this reduces the calcification rates of marine calcifying organisms, including planktic foraminifera. Such a reduction in calcification resulting from anthropogenic CO2 emissions has not been observed, or quantified in the field yet. Here we present the findings of a study in the Western Arabian Sea that uses shells of the surface water dwelling planktic foraminifer Globigerinoides ruber in order to test the hypothesis that anthropogenically induced acidification has reduced shell calcification of this species. We found that light, thin-walled shells from the surface sediment are younger (based on 14C and d13C measurements) than the heavier, thicker-walled shells. Shells in the upper, bioturbated, sediment layer were significantly lighter compared to shells found below this layer. These observations are consistent with a scenario where anthropogenically induced ocean acidification reduced the rate at which foraminifera calcify, resulting in lighter shells. On the other hand, we show that seasonal upwelling in the area also influences their calcification and the stable isotope (d13C and d18O) signatures recorded by the foraminifera shells. Plankton tow and sediment trap data show that lighter shells were produced during upwelling and heavier ones during non-upwelling periods. Seasonality alone, however, cannot explain the 14C results, or the increase in shell weight below the bioturbated sediment layer. We therefore must conclude that probably both the processes of acidification and seasonal upwelling are responsible for the presence of light shells in the top of the sediment and the age difference between thick and thin specimens.

Ba/Ca ratios in Neogloboquadrina pachyderma of sedimet core 94B17

Down-core samples of the planktonic foraminifer Neogloboquadrina pachyderma sinistral from the Mendeleyev Ridge in the western Arctic Ocean have been analyzed for Ba/Ca and d18O. The apparent distribution coefficient for N. pachyderma sin. is estimated at DBa = 0.22 ± 0.02. A meltwater event is identified at around 11.8 14C kyr BP and is coincident with elevated Ba/Ca ratios. The barium enrichment is believed to be the result of enhanced weathering and erosion following glaciation. Additionally, barium may have desorbed from shelf sediments as sea level rose. Changes in Ba/Ca correlate with the retreat of the Laurentide Ice Sheet and the evolution of the Mackenzie River drainage basin. Therefore maximum Ba/Ca in Arctic surface waters at 11.8 ka may be indicative of an increase in the export of freshwater from the Arctic to the North Atlantic, potentially contributing to the onset of the Younger Dryas. This work suggests that Ba/Ca in planktonic foraminifera may be a useful indicator of the timing and processes associated with deglaciation.

Age determination and pollen profile of sediment core Trentelmoor, Peine, northern Germany

The filling up of the lake which existed in the basin of the Trentelmoor (40 km E of Hannover, Germany) - in Preboreal times was finished 2000 years ago. Since then fen vegetation has covered the former lake's surface. The postglacial development of the vegetation follows the pattern which is typical of Central Europe. However, due to the poorness of the soils around the Trentelmoor, the frequencies of some tree species differ. Beech for example never reached - for the benefit of oak - that importance which this tree species usually gains on better soils. Human impact becomes recognisable in the upper Neolithic for the first time. The area has been settled continuously, but with changing intensities, throughout the last 3000 years. When the manuscript of this paper went to press the results of two radiocarbon age determinations only were completed. An additional three determinations were completed somewhat later. See the accompanying table for results.

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).

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

Geochemistry of interstitial gases in sedimentary deposits at DSDP Leg 64 Holes

We analyzed interstitial gases from holes at Sites 474, 477, 478, 479, and 481 in the Gulf of California, using gas chromatography and stable isotope mass spectrometry to evaluate their composition in terms of biogenic and thermogenic sources. The hydrocarbon gas (C1-C5) concentrations were comparable to the shipboard data, and no olefins could be detected. The ?13C data for the CH4 confirmed the effects of thermal stress on the sedimentary organic matter, because the values were typically biogenic near the surface and became more depleted in 12C versus depth in holes at Sites 474, 478, and 481. The CH4 at Site 477 was the heaviest, and in Hole 479 it did not show a dominant hightemperature component. The CO2 at depth in most holes was mostly thermogenic and derived from carbonates. The low concentrations of C2-C5 hydrocarbons in the headspace gas of canned sediments precluded a stable carbon-isotope analysis of their genetic origin.

Late Miocene development of the western Pacific warm pool: Planktonic foraminifer and oxygen isotopic evidence

The disappearance at ~10 Ma of the deep dwelling planktonic foraminifer Globoquadrina dehiscens from the western Pacific including the South China Sea was about 3 Myr earlier than its final extinction elsewhere. Accompanying this event at ~10 Ma was a series of faunal turnover characterized by increase in mixed layer, warm-water species and decrease to a minimum in deepwater species. Paleobiological and isotopic evidence indicates sea surface warming and a deepened local thermocline that we interpret as related to the development of an early western Pacific warm pool. The stepwise decline of G. dehiscens and other deep dwelling species from the NW and SW Pacific suggests more intensive warm water pileup than equatorial localities where surface bypass flow through the narrowing Indonesia seaway appears to remain efficient during the late Miocene. Planktonic delta18O values from the South China Sea consistently lighter than the tropical western Pacific during the Miocene also suggest, similar to today, more variable hydrologic conditions along the periphery than in the core of the warm pool. Stronger hydrologic variability affected mainly by monsoons and increased thermal gradient along the western margin of the late Miocene warm pool may have contributed to the decline of deep dwelling planktonic species including the early extinction of G. dehiscens from the South China Sea region. The late Miocene warm pool became influential and paleobiologically detectable from ~10 Ma, but the modern warm pool did not appear until about 4 Ma, in the middle Pliocene.

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 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.