Stable oxygen and carbon isotopes and sediment geochemistry of sediment core GeoB12616-4

The Indian Ocean is an important component of the global thermohaline circulation system, as its western boundary currents feed the Agulhas Current, an integral part of the Atlantic meridional overturning circulation. However, Indian Ocean intermediate to deep-water variability on glacial-interglacial timescales is still a matter of debate. Here we provide stable carbon and oxygen isotopes and sediment elemental compositions of a sediment core from the edge of the Somali Basin. We demonstrate that throughout the past 600 kyr the intermediate western Indian Ocean was primarily bathed by Southern Ocean sourced Upper Circumpolar Deep Water (UCDW). This Southern Ocean sourced water mass enters the Somali Basin via the Amirante Passage or the Mozambique Channel and represents a downstream equivalent of South Atlantic UCDW. We cannot clearly account for the shortterm passage of Red Sea Water (RSW) at 1500 m water depth along the African continental margin, as previously suggested, on glacial-interglacial timescales.

Sedimentology and geochemistry of core GIK23258-2 in the Barents Sea

At the western continental margin of the Barents Sea, 75°N, hemipelagic sediments provide a record of Holocene climate change with a time resolution of 10-70 years. Planktic foraminifera counts reveal a very early Holocene thermal optimum 10.7-7.7 kyr BP, with summer sea surface temperatures (SST) of 8°C and a much enhanced West Spitsbergen Current. There was a short cooling between 8.8 and 8.2 kyr BP. In the middle and late Holocene summer, SST dropped to 2.5°-5.0°C, indicative of reduced Atlantic heat advection, except for two short warmings near 2.2 and 1.6 kyr BP. Distinct quasi-periodic spikes of coarse sediment fraction (with large portions of lithic grains, benthic and planktic foraminifera) record cascades of cold, dense winter water down the continental slope as a result of enhanced seasonal sea ice formation and storminess on the Barents shelf over the entire Holocene. The spikes primarily cluster near recurrence intervals of 400-650 and 1000-1350 years, when traced over the entire Holocene, but follow significant 885-/840- and 505-/605-year periodicities in the early Holocene. These non-stationary periodicities mimic the Greenland-[Formula: See Text]Be variability, which is a tracer of solar forcing. Further significant Holocene periodicities of 230, (145) and 93 years come close to the deVries and Gleissberg solar cycles.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Carbon geochemistry of marine sediment south of Barbados

Isotopic and geochemical proxies measured in bulk sediment samples of two gravity cores south of Barbados were used to develop a model for the organic carbon accumulation during the last 250 kyr with respect to the influence of terrestrial sources (e.g. the Orinoco and Amazon rivers) as well as the marine contributions, sea-level, surface currents, and morphological features. Total organic carbon (TOC) content and the stable organic carbon isotopes of the organic matter (delta13Corg) show no glacial to interglacial variability. TOC content is generally very low in both cores but increases between 40 and 120 kyr. A comparable pattern is detected in accumulation rates of the organic matter but is only hinted in the delta13Corg ratios. The results suggest that during the last 250 kyr the organic carbon accumulation south of Barbados has been controlled by glacioeustatic sea-level changes and the general morphologic settings. A sea-level stand of 15-80 m below present day seems generally to favour the accumulation of organic matter south of Barbados. Although delta13Corg ratios reveal no clear trend in the organic matter composition, terrestrial organic carbon discharged by rivers (Orinoco or Amazon) seems not to be a major component in the sediments of that area during the last 250 kyr.

Calcareous dinoflagellate cysts and geochemistry of Mediterranean Sea sediments

Comparison of calcareous dinoflagellate cyst assemblages with Ba, Al, Mn, and Fe records from three sediment cores collected in the eastern Mediterranean Sea indicate that calcareous dinoflagellate cysts are generally resistant to postdepositional dissolution. Cyst association changes during and after sapropel S1 formation can therefore be closely related to variability in surface water productivity. Two groups of cysts are defined: those having highest abundances within the sapropelic and postsapropelic sediments. The temporal cyst distributions suggest increased freshwater input mainly from the Nile and a shallowing of the pycnocline as the most important processes increasing nutrient concentration in the photic zone, thus leading to increased productivity and organic carbon fluxes during sapropel formation. Furthermore, a general warming trend at the beginning of S1 formation and a slight salinity decrease are reconstructed.

Geochemistry on sapropel deposition in the eastern Mediterranean from cores TTR-GL94 and M25/4-KL11

The geochemistry of the youngest Mediterranean sapropel layer suggests changes in productivity and water column oxygen conditions during sapropel deposition. The Ba-enriched interval is broader than the organic-carbon-rich interval of this sapropel. We suggest that the Ba-enriched horizon records the original thickness of the sapropel prior to subsequent partial oxidation. The main carrier of Ba is barite, as microcrystals (0.5-5 µm ) having a morphology characteristic of marine barite, particularly abundant beneath high productivity regions. Ba concentrations do not change at the sapropel layer oxidation front and diagenetic barite crystals are absent, thus the Ba-enriched layer reflects original oceanic conditions of increased biological productivity during sapropel deposition and not diagenetic Ba remobilization. Paleoredox indicators point to restricted oxygenated bottom water but not to fully anoxic conditions. Detrital elements within this layer indicate a lower eolian terrigenous input, enhanced humidity, and increased precipitation/runoff, thus likely higher nutrient supply.

Geochemistry of sediment core GeoB7920-2

The X-ray fluorescence (XRF) core scanner provides bulk-sediment chemistry data measured nondestructively at the split core sediment surface. Although this method is widely accepted, there is little known about the effects of physical properties such as density and water content on XRF core scanner data. Comparison of XRF scanner measurements from the sediment surface and dry powder samples of sediment core GeoB7920 indicates strongly reduced element intensities for the lighter elements Al and Si. We relate the lower element intensities of the measurements taken at the sediment surface to the amount of water in the sample volume analyzed by the XRF core scanner. The heavier elements K, Ca, Ti, and Fe remain relatively unaffected by the variation of any physical property within sediment core GeoB7920. Additionally, we successfully use the elemental intensity of Cl as a proxy for the seawater content in the sample volume analyzed by the XRF core scanner. This enables the establishment of a correction function for the elements Al and Si that corrects for the radiation absorption of the water content in sediment core GeoB7920 off Cape Blanc, NW Africa.