Sulfur isotope composition of pore fluids at ODP Sites 128-798 and 128-799

Micro-crystalline barites recovered by deep-sea drilling from Site 684 on the Peru margin and Site 799 in the Japan Sea are highly enriched in the heavy sulfur isotope relative to seawater ( d34S up to +84?). This isotopic composition is consistent with remobilization of biogenic barite triggered by sulfate reduction, and subsequent reprecipitation as a diagenetic barite front. The high levels of barium sulfate in these deposits (10-50%) cannot be explained by a diffusive transport model in sediments experiencing a constant rate of sedimentation. When sedimentation rates change radically, the barite front will remain at a given depth interval leading to large accumulations of barium sulfate. Such conditions may have generated the barite deposits at Site 799. At Site 684, on the other hand, there is evidence that the barite deposits are a result of the tectonically-driven advection of sulfate-bearing fluids through the sediment column.

Measurements of stable carbon isotope ratios of CO2 over the last 24000 years and CO2 concentration measurements on Antarctic ice cores using three different methods

The stable carbon isotope ratio of atmospheric CO2 (d13Catm) is a key parameter in deciphering past carbon cycle changes. Here we present d13Catm data for the past 24,000 years derived from three independent records from two Antarctic ice cores. We conclude that a pronounced 0.3 per mil decrease in d13Catm during the early deglaciation can be best explained by upwelling of old, carbon-enriched waters in the Southern Ocean. Later in the deglaciation, regrowth of the terrestrial biosphere, changes in sea surface temperature, and ocean circulation governed the d13Catm evolution. During the Last Glacial Maximum, d13Catm and atmospheric CO2 concentration were essentially constant, which suggests that the carbon cycle was in dynamic equilibrium and that the net transfer of carbon to the deep ocean had occurred before then.

Os isotope ratios of sediments from the Eocene-Oligocene boundary

Osmium (Os) isotope analyses of bulk sediments from the South Atlantic, Equatorial Pacific, and the Italian Apennines yield a well-dated and coherent pattern of 187Os/188Os variation from the late Eocene to the early Oligocene. The resulting composite record demonstrates the global character of two prominent features of the low-resolution LL44-GPC3 Os isotope record (Pegram and Turekian, 1999, doi:10.1016/S0016-7037(99)00308-7). These are: (1) a pronounced minimum in 187Os/188Os (0.22-0.27) in the late Eocene, between 34 and 34.5 Ma, and (2) a subsequent rapid increase in 187Os/188Os, to approximately 0.6 by 32 Ma. An ultramafic weathering event and an increased influx of extraterrestrial particles to the Earth are discussed as alternative explanations for the late Eocene 187Os/188Os minimum. Comparison of the 187Os/188Os to benthic foraminiferal oxygen isotope records demonstrates that the nearly three-fold increase in 187Os/188Os from the late Eocene minimum coincides with the growth and decay of the first large ice sheet of the Oligocene (Oi1 (Miller et al., 1991, doi:10.1029/90JB02015)). The fine structure of the Os isotope record indicates that enhanced release of radiogenic Os, unrelated to the recovery from late Eocene minimum, lagged the initiation of the Oi1 event by roughly 0.5 Myr. This record, in conjunction with weathering studies in modern glacial soils (Blum, in: W.F. Ruddiman (Ed.), Tectonic Uplift and Climate Change, Plenum Press, New York, 1997, pp. 259-288; Peucker-Ehrenbrink and Blum, 1998, doi:10.1016/S0016-7037(98)00227-0), suggests that exposure of freshly eroded material during deglaciation following Oi1 enhanced chemical weathering rates, and may have contributed to ice sheet stabilization by drawing down atmospheric carbon dioxide. The improved temporal resolution and age control of the refined Eocene-Oligocene Os isotope record also makes it possible to illustrate the late Eocene Os isotope excursion as a tool for global correlation of marine sediments.

Strontium-isotope stratigraphy and oxygen- and carbon-isotope record of Middle Jurassic to Early Cretaceous belemnites in the South Atlantic

87Sr/86Sr data of belemnites are presented from a Middle Jurassic-Early Cretaceous succession from the Falkland Plateau (Deep Sea Drilling Project Sites 511 and 330) that was deposited in a periodically anoxic, semi-enclosed shallow water basin. Diagenetically screened strontium-isotope values of 0.706789 rise to 0.707044 before increasing sharply to 0.707428 in the uppermost part of the sampled succession. Comparison with published strontium calibration curves suggests that the oldest samples were Callovian to Oxfordian in age, whilst the remainder of the Jurassic part of the succession consisted of Kimmeridgian and Early Tithonian age sediments. The nannofossil, dinoflagellate and molluscan assemblages provide comparable age determinations. The strontium-isotope analysis of the youngest belemnites points to a Hauterivian-Barremian age, whilst age interpretations based upon the fauna provide a wide age range from the Barremian to early Albian. Strontium-isotope stratigraphy of this succession hence offers increased age resolution providing data regarding the timing of episodes of bottom water anoxia which have been recorded throughout the South Atlantic Basin. Well-preserved belemnite specimens display an oxygen-isotope range between +0.08 and -2.22? (PDB, Peedee belemnite international standard) and a carbon-isotope range from +2.35 to -1.33? (PDB). Delta13C values become increasingly negative through the Late Jurassic-Early Cretaceous and in concert with the 87Sr/86Sr data reveal a trend that could be accounted for by increasing levels of weathering and erosion. The oxygen-isotope data if interpreted in terms of palaeotemperature are consistent with warm palaeotemperatures in the Kimmeridgian and slightly cooler temperatures for the Tithonian and Early Cretaceous parts of the succession. The proposed relative Kimmeridgian warmth (based upon strontium-isotope age assignments) is thus in good agreement with other published palaeotemperature records.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers of surface sediment samples

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3 - 4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4 per mil lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, d44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal d44/40Ca and Sr/Ca proxy signals.

Stable isotope stratigraphy of ODP Site 167-1014

Late Quaternary oxygen (d18O) and carbon (d13C) isotopic records for the benthic foraminifer Uvigerina and the planktonic foraminifer Globigerina bulloides are presented for the upper 20 meters composite depth sediment sequence of Ocean Drilling Program Site 1014, Tanner Basin, in the outer California Borderland province. The benthic oxygen isotopic record documents a continuous >160-k.y. sequence from marine isotope Stage (MIS) 6 to the present day. The record closely resembles other late Quaternary North Pacific benthic isotope records, as well as the well-dated deep-sea sequence (SPECMAP), and thus provides a detailed chronologic framework. Site 1014 provides a useful record of the California response to climate change as it enters the southern California Border-land. Sedimentation rates are relatively constant and high (~11.5 cm/k.y. ). The planktonic foraminiferal record is well pre-served except during marine isotope Substages 5b and 5d, when normally high G. bulloides abundance is strongly diminished as a result of dissolution. The planktonic oxygen isotopic shift of ~3 per mil between the last glacial maximum and the Holocene suggests a surface water temperature shift of <7°C, similar to estimates from Hole 893A (Leg 146) to the north. Unlike Santa Barbara Basin, G. bulloides d18O values during the last interglacial (MIS 5) at Site 1014 were significantly higher than during the Holocene. In particular, marine isotope Substage 5e (Eemian) was ~0.8 per mil higher. This is unlikely to reflect a cooler Eemian but is instead the result of preferential dissolution of thin-shelled (low d18O) specimens during this interval. In this mid-depth basin, a large benthic d18O shift during Termination I suggests dramatic temperature and salinity changes in response to switches in the source of North Pacific Intermediate Water. Although d13C values of the planktonic foraminifer G. bulloides are in disequilibria with seawater and hence interpretations are limited, the G. bulloides record exhibits several negative d13C excursions found at other sites in the region (Sites 1017 and 893). This indicates a response of G. bulloides d13C to regional surface water processes along the southern California margin. A general increase in benthic carbon isotopic values (-1.75 per mil to -0.75 per mil) in Tanner Basin during the last 200 k.y. is overprinted with smaller fluctuations correlated with climate change. The coolest intervals during the last glacial maximum (MISs 2 and 4) exhibit lower benthic d13C values, which correlate with global 13C shifts. The opposite relationship is exhibited during the last interglacial before 85 ka, when lower benthic d13C values are associated with warmer intervals (marine isotope Substages 5c and 5e) of the last interglacial. These time intervals were also marked by decreased intermediate water ventilation. Increased dissolution and organic accumulation during Substages 5b and 5d are anticorrelated with the benthic d13C record. These results suggest that a delicate balance in intermediate water d13C has existed between the relative influences of global 13C and regional ventilation changes at the 1165-m water depth of Site 1014.

Age models and stable isotope analysis on sediment core Site 199-1218 from the equatorial Pacific

A 13-million-year continuous record of Oligocene climate from the equatorial Pacific reveals a pronounced "heartbeat" in the global carbon cycle and periodicity of glaciations. This heartbeat consists of 405,000-, 127,000-, and 96,000-year eccentricity cycles and 1.2-million-year obliquity cycles in periodically recurring glacial and carbon cycle events. That climate system response to intricate orbital variations suggests a fundamental interaction of the carbon cycle, solar forcing, and glacial events. Box modeling shows that the interaction of the carbon cycle and solar forcing modulates deep ocean acidity as well as the production and burial of global biomass. The pronounced 405,000-year eccentricity cycle is amplified by the long residence time of carbon in the oceans.

Climate reconstruction and oxygen isotope composition of sediment core Dethlingen, Germany

To gain insights into the mechanisms of abrupt climate change within interglacials, we have examined the characteristics and spatial extent of a prominent, climatically induced vegetation setback during the Holsteinian interglacial (Marine Isotope Stage 11c). Based on analyses of pollen and varves of lake sediments from Dethlingen (northern Germany), this climatic oscillation, here termed the "Older Holsteinian Oscillation" (OHO), lasted 220 years. It can be subdivided into a 90-year-long decline of temperate tree taxa associated with an expansion of Pinus and herbs, and a 130-year-long recovery phase marked by the expansion of Betula and Alnus, and the subsequent recovery of temperate trees. The climate-induced nature of the OHO is corroborated by changes in diatom assemblages and ?18O measured on biogenic silica indicating an impact on the aquatic ecosystem of the Dethlingen paleolake. The OHO is widely documented in pollen records from Europe north of 50° latitude and is characterized by boreal climate conditions with cold winters from the British Isles to Poland, with a gradient of decreasing temperature and moisture availability, and increased continentality towards eastern Europe. This pattern points to a weakened influence of the westerlies and/or a stronger influence of the Siberian High. A comparison of the OHO with the 8.2 ka event of the Holocene reveals close similarities regarding the imprint on terrestrial ecosystems and the interglacial boundary conditions. Hence, in analogy to the 8.2 ka event, a transient, meltwater-induced slowdown of the North Atlantic Deep Water formation appears as a plausible trigger mechanism for the OHO. If correct, meltwater release into the North Atlantic may be a more common agent of abrupt climate change during interglacials than previously thought. We conclude that meltwater-induced climate setbacks during interglacials preferentially occurred when low rates of summer insolation increase during the preceding terminations facilitated the persistence of large-scale continental ice-sheets well into the interglacials.