Elemental and stable isotopic composition of fine fraction samples of ODP Site 115-709 (Table 1)

Stable isotopic and minor element compositions were measured on the fine fraction of pelagic carbonate sediments from Ocean Drilling Program Site 709 in the central Indian Ocean. This section ranges in age from 47 Ma to the present. The observed compositional variations are the result of either paleoceanographic changes (past oceanic chemical or temperature variations) or diagenetic changes. The CaCO3 record is little affected by diagenesis. From previous work, carbonate content is known to be determined by the interplay of biological productivity, water column dissolution, and dilution. The carbon isotopic record is generally similar to previously published curves. A good correlation was observed between sea-level high stands and high 13C/12C ratios. This supports Shackleton's hypothesis that as the proportion of organic carbon buried in marine sediments becomes larger, oceanic-dissolved inorganic carbon becomes isotopically heavier. This proportion appears to be higher when sea level is higher and organic carbon is buried in more extensive shallow-shelf sediments. The strontium content and oxygen isotopic composition of carbonate sediments are much more affected by burial diagenesis. Low strontium concentrations are invariably associated with high values of d18O, probably indicating zones of greater carbonate recrystallization. Nevertheless, there is an inverse correlation between strontium concentration and sea level that is thought to be a result of high-strontium aragonitic sedimentation on shallow banks and shelves during high stands. Iron and manganese concentrations and, to a lesser extent, magnesium and strontium concentrations and carbon isotopic ratios are affected by early diagenetic reactions. These reactions are best observed in a slumped interval of sediments that occurs between 13.0 and 17.5 Ma. As a result of microbial reduction of manganese and iron oxides and dissolved sulfate, it is hypothesized that small amounts of mixed-metal carbonate cements are precipitated. These have low carbon isotopic ratios and high concentrations of metals.

Geochemistry, grain sizes and radiocarbon age of sediment core Lz1005 from Amery Oasis, East Antarctica

The clay mineralogical composition of a 552 cm long sediment core from Lake Terrasovoje in Amery Oasis, East Antarctica, was analysed and compared with that in surface sediments from other locations in the vicinity. The lower part of the sediment core is formed by sub- and proglacial sediments with a dominance of smectite and illite, and lower amounts of kaolinite and chlorite. The upper part of the core is deposited after 12 500 cal yr bp and mainly composed of illite and kaolinite, with low amounts of smectite and chlorite, such as found in samples from rock outcrops and covering sediments throughout Amery Oasis. The clay composition in the lower section of core Lz1005 suggest that the basin of Lake Terrasovoje was filled by a 150-200 m thickened Nemesis Glacier prior to 12 500 cal yr bp rather than by local ice caps.

Radiocarbon age determinations of coral and reef cores from the Philippines off North Bohol and Olango

Nine holes were drilled with a submersible hydraulic drill into the slopes and reef flats of the Caubyan and Calituban reefs as well as of Olango Flat. The maximum depth of core penetration was 11 m. 14C ages showed that the Caubyan and Calituban reefs were formed within the last 6,000 years. Corals settled on a pre-existing relief parallel to the island of Bohol, building a framework for other carbonate-producing organisms. The reef flat south of Olango has a different structure. Formation took place during a Pleistocene high sea level, e.g. 125,000 years ago.

Stable isotopes and XRF data over the Paleocene-Eocene Thermal Maximum from IODP Sites U1403 and U1409

During the Paleocene-Eocene Thermal Maximum (PETM) about 56 million years ago, thousands of petagrams of carbon were released into the atmosphere and ocean in just a few thousand years, followed by a gradual sequestration over approximately 200,000 years. If silicate weathering is one of the key negative feedbacks that removed this carbon, a period of seawater calcium carbonate saturation greater than pre-event levels is expected during the event's recovery phase. In marine sediments, this should be recorded as a temporary deepening of the depth below which no calcite is preserved - the calcite compensation depth (CCD). Previous and new sedimentary records from sites that were above the pre-PETM calcite compensation depth show enhanced carbonate accumulation following the PETM. A new record from an abyssal site in the North Atlantic that lay below the pre-PETM calcite compensation depth shows a period of carbonate preservation beginning about 70,000 years after the onset of the PETM, providing the first direct evidence for an over-deepening of the calcite compensation depth. This record confirms an overshoot in ocean carbonate saturation during the PETM recovery. Simulations with two earth system models support scenarios for the PETM that involve both a large initial carbon release followed by prolonged low-level emissions, consistent with the timing of CCD deepening in our record. Our findings indicate that sequestration of these carbon emissions was most likely the result of both globally enhanced calcite burial above the calcite compensation depth and, at least in the North Atlantic, by a temporary over-deepening of the calcite compensation depth.

Stable carbon isotope record and geochemistry of late Miocene-early Pliocene sediments from DSDP Site 90-590 in the Tasman Sea

Biogenic components of sediment accumulated at high rates beneath frontal zones of the Indian and Pacific oceans during the late Miocene and early Pliocene. The delta13C of bulk and foraminiferal carbonate also decreased during this time interval. Although the two observations may be causally linked, and signify a major perturbation in global biogeochemical cycling, no site beneath a frontal zone has independent records of export production and delta13C on multiple carbonate phases across the critical interval of interest. Deep Sea Drilling Project (DSDP) site 590 lies beneath the Tasman Front (TF), an eddy-generating jetstream in the southwest Pacific Ocean. To complement previous delta13C records of planktic and benthic foraminifera at this location, late Neogene records of CaCO3 mass accumulation rate (MAR), Ca/Ti, Ba/Ti, Al/Ti, and of bulk carbonate and foraminiferal delta13C were constructed at site 590. The delta13C records include bulk sediment, bulk sediment fractions (<63 µm and 5-25 µm), and the planktic foraminifera Globigerina bulloides, Globigerinoides sacculifer (with and without sac), and Orbulina universa. Using current time scales, CaCO3 MARs, Ca/Ti, Al/Ti and Ba/Ti ratios are two to three times higher in upper Miocene and lower Pliocene sediment relative to overlying and underlying units. A significant decrease also occurs in all delta13C records. All evidence indicates that enhanced export production - the 'biogenic bloom' - extended to the southwest Pacific Ocean between ca. 9 and 3.8 Ma, and this phenomenon is coupled with changes in delta13C - the 'Chron C3AR carbon shift'. However, CaCO3 MARs peak ca. 5 Ma whereas elemental ratios are highest ca. 6.5 Ma; foraminiferal delta13C starts to decrease ca. 8 Ma whereas bulk carbonate delta13C begins to drop ca. 5.6 Ma. Temporal discrepancies between the records can be explained by changes in the upwelling regime at the TF, perhaps signifying a link between changes in ocean-atmosphere circulation change and widespread primary productivity.

Stable carbon and oxygen isotope ratios of bulk sediment from DSDP Hole 62-463 (Appendix A)

In order to elucidate early Aptian marine paleotemperature evolution across the period of enhanced organic carbon (Corg)-burial [Oceanic Anoxic Event (OAE) 1a], stable isotope analyses were performed on pelagic limestones at Deep Sea Drilling Project Site 463, central Pacific Ocean. The delta18O data exhibit a distinct anomaly by ~-2? spanning the OAE 1a interval (i.e., a ~6 m-thick, phytoplanktonic Corg-rich unit constrained by magneto-, bio- and delta13C stratigraphy). Elucidation of paleotemperature significance of the delta18O shift is made by taking account of recent Sr/Ca evidence at the same section, which revealed that geochemical signals in carbonate-poor lithologies are relatively unaltered against burial diagenesis. By discriminating delta18O values from carbonate-poor samples (CaCO3 contents=5-30 wt.%), it appears that an abrupt rise in seasurface temperatures (SSTs) by 8 °C (=-1.7? shift in delta18O) occurred immediately before OAE 1a, whereas a cooling mode likely prevailed during the peak Corg-burial. In terms of its stratigraphic relationship as to the Corg-rich interval and to a pronounced negative delta13C excursion, as well as its timescale, the observed SST rise resembles those associated with the Paleocene-Eocene thermal maximum and, more strikingly, Jurassic Toarcian OAE. This observation is consistent with the hypothesis that these paleoenvironmental events were driven by a common causal mechanism, which was likely initiated by the greenhouse effect via massive release of CH4 or CO2 from the isotopically-light carbon reservoir and terminated by a negative productivity feedback.

(Table 3) Relative depth and age, CaCO3, d18O, d13C and Sr/Ca analysis from ODP Leg 130, 154 and 138

Interpretations of calcite strontium/calcium records in terms of ocean history and calcite diagenesis require distinguishing the effects on deep-sea calcite sediments of changes in ocean chemistry, of different mixes of calcite-depositing organisms as sediment contributors through time and space, and of the loss of Sr during diagenetic calcite recrystallization. In this paper Sr/Ca and d18O values of bulk calcium carbonate sediments are used to estimate the relative extent of calcite recrystallization in samples from four time points (core tops, 5.6, 9.4, and 37.1 Ma) at eight Ocean Drilling Program sites in the equatorial Atlantic (Ceara Rise) and equatorial Pacific (Ontong Java Plateau and two eastern equatorial Pacific sites). The possibility that site-to-site differences in calcite Sr/Ca at a given time point originated from temporal variations in ocean chemistry was eliminated by careful age control of samples for each time point, with sample ages differing by less than the oceanic residence times of Sr and Ca. The Sr/Ca and d18O values of 5.6- and 9.4-Ma samples from the less-carbonate-rich eastern equatorial Pacific sites and Ceara Rise Site 929 appear to be less diagenetically altered than the Sr/Ca and d18O values of contemporaneous samples from the more carbonate-rich sites. It is evident from these data that both Sr/Ca and d18O in bulk calcite have been diagenetically altered in some samples 5.6 Ma and older. These data indicate that noncarbonate sedimentary components, like clay and biogenic silica, have partially suppressed recrystallization at the lower carbonate sites. Sr/Ca data from the less altered, carbonate-poor sites indicate higher oceanic Sr/Ca relative to today at 5.6 and 9.4 Ma.

Composition of sediments from the Arabian Sea

Thirty seven deep-sea sediment cores from the Arabian Sea were studied geochemically (49 major and trace elements) for four time slices during the Holocene and the last glacial, and in one high sedimentation rate core (century scale resolution) to detect tracers of past variations in the intensity of the atmospheric monsoon circulation and its hydrographic expression in the ocean surface. This geochemical multi-tracer approach, coupled with additional information on the grain size composition of the clastic fraction, the bulk carbonate and biogenic opal contents makes it possible to characterize the sedimentological regime in detail. Sediments characterized by a specific elemental composition (enrichment) originated from the following sources: river suspensions from the Tapti and Narbada, draining the Indian Deccan traps (Ti, Sr); Indus sediments and dust from Rajasthan and Pakistan (Rb, Cs); dust from Iran and the Persian Gulf (Al, Cr); dust from central Arabia (Mg); dust from East Africa and the Red Sea (Zr/Hf, Ti/Al). Corg, Cd, Zn, Ba, Pb, U, and the HREE are associated with the intensity of upwelling in the western Arabian Sea, but only those patterns that are consistently reproduced by all of these elements can be directly linked with the intensity of the southwest monsoon. Relying on information from a single element can be misleading, as each element is affected by various other processes than upwelling intensity and nutrient content of surface water alone. The application of the geochemical multi-tracer approach indicates that the intensity of the southwest monsoon was low during the LGM, declined to a minimum from 15,000-13,000 14C year BP, intensified slightly at the end of this interval, was almost stable during the Bölling, Alleröd and the Younger Dryas, but then intensified in two abrupt successions at the end of the Younger Dryas (9900 14C year BP) and especially in a second event during the early Holocene (8800 14C year BP). Dust discharge by northwesterly winds from Arabia exhibited a similar evolution, but followed an opposite course: high during the LGM with two primary sources-the central Arabian desert and the dry Persian Gulf region. Dust discharge from both regions reached a pronounced maximum at 15,000-13,000 14C year. At the end of this interval, however, the dust plumes from the Persian Gulf area ceased dramatically, whereas dust discharge from central Arabia decreased only slightly. Dust discharge from East Africa and the Red Sea increased synchronously with the two major events of southwest monsoon intensification as recorded in the nutrient content of surface waters. In addition to the tracers of past dust flux and surface water nutrient content, the geochemical multi-tracer approach provides information on the history of deep sea ventilation (Mo, S), which was much lower during the last glacial maximum than during the Holocene. The multi-tracer approach-i.e. a few sedimentological parameters plus a set of geochemical tracers widely available from various multi-element analysis techniques-is a highly applicable technique for studying the complex sedimentation patterns of an ocean basin, and, specifically in the case of the Arabian Sea, can even reveal the seasonal structure of climate change.

Isotopes content, mineralogical composition, Uranium and Thorium contents and determined activity ratios from METEOR cruise M74/3 in 2007

Authigenic carbonate deposits have been sampled with the remotely operated vehicle 'MARUM-QUEST 4000 m' from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The delta18O carbonate values range from 1.3 to 4.2 per mil V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low delta13Ccarbonate values (as low - 54.6per mil V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by delta13C methane values ranging from - 70.3 to - 66.7per mil V-PDB, and also by back-calculations considering delta 13C methane values of carbonate and incorporated lipid biomarkers.

Termination II record, stable isotopes and trace elements of Stagamite MF-3 from Schafsloch Cave

The timing and nature of the penultimate deglaciation, also known as Termination II (T-II), is subject of controversial discussions due to the scarcity of precisely-dated palaeoclimate records. Here we present a new precisely-dated and highly-resolved multi-proxy stalagmite record covering T-II from the high alpine Schafsloch Cave in Switzerland, an area where climate is governed by the North Atlantic. The inception of stalagmite growth at 137.4 ± 1.4 kyr before present (BP) indicates the presence of drip water and cave air temperatures of above 0 °C, and is related to a climate-induced change in the thermal state (from cold-to warm-based) of the glacier above the cave. The cessation of stalagmite growth between 133.1 ± 0.7 and 131.9 ± 0.6 kyr BP is most likely related to distinct drop in temperature associated with Heinrich stadial 11. The resumption of stalagmite growth at 131.9 ± 0.6 kyr BP is accompanied by an abrupt increase in temperature and precipitation as indicated by distinct shifts in the oxygen and carbon isotopic composition as well as in trace element concentrations. The mid-point of T-II is around 131.8 ± 0.6 kyr BP in the Schafsloch Cave record is significantly earlier compared to the age of 129.1 ± 0.1 kyr BP in the Sanbao Cave record from China. The different ages between both records can be best explained by the competing effects of insolation and glacial boundary forcing on seasonality and snow cover extent in Eurasia.