(Table 1) Sapropel analysis from ODP Sites 160-964, 160-966, 160-967 and 160-969

Seventeen eastern Mediterranean Pliocene sapropels from ODP Sites 964, 966, 967 and 969, some of which are coeval, have been analysed for their geochemistry. The sapropels are characterized by very high organic carbon contents (up to 30%) which are reported to be the result of both increased productivity and improved preservation. Although the organic matter in the sapropels is mainly of marine origin, the d13Corg values and C/N ratios appear "terrestrial". This is the result of anaerobic organic matter degradation which preferentially removed nitrogen- and 13C-rich organic components. A comparison with Ti/Al profiles, which mimic the precession index, and a calculation of organic carbon accumulation rates indicate that sedimentation rates were at most 30% lower or at most 50% higher during sapropel formation. Thus, sapropel formation lasted from between 2000 and 10,000 years at Site 964 to between 4500 and 12,000 years at Site 967. A synthesis of new data and a comparison with existing models indicates that productivity, which increased due to extra nutrients supplied as a result of winter mixing and as a result of enhanced input by the Nile, was the driving mechanism behind sapropel formation. The resulting sapropel formation was simultaneous at different depths, but lasted longer in the part of the basin closest to the Nile.

(Appendix) Carbon and nitrogen isotope ratios of ODP Site 160-964

Nitrogen isotopes of chlorins, degradation products of chlorophyll, reflect the isotopic composition of nutrient N utilized by marine phytoplankton communities. Here we show that in sediments of the eastern Mediterranean Pleistocene and Holocene, values of d15N for chlorins and total nitrogen vary in concert, with a consistent offset of ~5 per mil reflecting the fractionation imparted during chlorophyll biosynthesis. Samples from the Integrated Ocean Drilling Program Sites 964 and 969 were analyzed at a sampling resolution of ~4-10 cm, clustered around sapropel events 2, 3, 4 and 5 (~100-170 ka). In low organic content sediments, chlorin values of ~0 per mil coincident with total nitrogen values of ~+ 5 per mil indicate that the latter reflects the original biomass and is not a consequence of diagenetic isotope enrichment. In sapropel horizons, the chlorin and total nitrogen values are 5 per mil more negative (~-5 per mil and ~ 0 per mil, respectively), resembling previously-reported, modern-day water-column particulates (~0 per mil). We suggest that nutrient conditions in the Eastern Mediterranean correspond to three scenarios and that the similarity between sapropel and modern-day bulk d15N is coincidental. Organic-poor marl sediments formed under oligotrophic conditions where surface productivity resulted from upwelling of Atlantic-sourced nitrate. Sapropels were characterized by enhanced diazotrophy that was likely fueled by increased riverine P fluxes to surface waters. Present-day conditions are dominated by anthropogenic N sources. These scenarios agree with a model of sapropel formation in which stratification caused by increased fresh-water inputs led to N fixation due to P:N nutrient imbalance. Enhanced production combined with stratification promoted and maintained anoxic deep waters, consequently increasing organic matter preservation. Such a model may be relevant to interpreting other episodes of intense organic matter deposition in past oceans.

The sapropel record of the eastern Mediterranean Sea

Research on sediments recovered during Ocean Drilling Leg 160 has concentrated on two issues: the first concerned the stratigraphy of sapropel formation, the second was oriented to clarify specific processes that explain sapropel origin. Progress has been made in the construction of stratigraphic composites out of sedimentary sequences from individual holes at each of the palaeoceanographic sites. On the composites, initial work has resulted in the establishment of high-resolution and intermediate-resolution stratigraphies for three sites (963, 964, 967); correlation of sedimentary cycles to astronomical (insolation) cycles extends the stratigraphies to Sites 969 and 966. The sapropel occurrences in the marine and land sequences over the entire Eastern Mediterranean are correlated; with the resolution that can be obtained from isotope studies, groups of sapropels occurred simultaneously over the entire basin. In detail, however, the temporal and facies patterns of sapropel sequences differ between individual sites and depositional basins. The differences may be related to effects of water depth, diagenesis, and post-depositional tectonic attenuation of sequences. Studies on the geochemistry and facies of sapropels agree that anoxic conditions favoured preservation of organic matter in sapropels, caused the enrichment of trace metals associated with sapropels, and helped to preserve primary sedimentary structures. Besides, all evidence is consistent with elevated fluxes of organic matter and associated elements during sapropel events.

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Calcareous nannofossil bioevents of early-middle Pleistocene sediments from the Mediterranean Sea and the Noth Atlantic

Quantitative distributions of calcareous nannofossils are analysed in the early-middle Pleistocene at the small Gephyrocapsa and Pseudoemiliania lacunosa zone transition in deep-sea cores from the Mediterranean Sea and North Atlantic Ocean (Ocean Drilling Program [ODP] Sites 977, 964 and 967, Deep Sea Drilling Project [DSDP] Site 607). The temporal and spatial mode of occurrence of medium-sized gephyrocapsids and reticulofenestrids has been examined to refine biostratigraphic constraints and evaluate possible relationships of stratigraphic patterns to environmental changes during a period of global climatic deterioration. The timing of bioevents has been calibrated using high-resolution sampling and correlation to the delta18O record in chronologically well-constrained sections. Newly identified events and ecostratigraphical signals enhance the stratigraphic resolution at the early-middle Pleistocene. The first occurrence (FO) of intermediate morphotypes between Pseudoemiliania and Reticulofenestra (Reticulofenestra sp.) is proposed as a reliable event within marine isotope stage (MIS) 35 or at the MIS 35/34 transition. The distribution of Reticulofenestra asanoi is characterized by rare and scattered occurrences in its lowest range, but the first common occurrence (FCO) is consistently identified at MIS 32 or 32/31; the last common occurrence (LCO) of the species is a distinctive event at MIS 23. In the studied interval, Gephyrocapsa omega dominates among medium-sized Gephyrocapsa. The FO of G. omega and contemporaneous re-entry of medium-sized gephyrocapsids at the lower-middle Pleistocene transition are diachronous between the Atlantic Ocean and Mediterranean Sea and from the western to eastern Mediterranean. In the Mediterranean, the LO of G. omega falls at MIS 15, insolation cycle 54 and is isochronous among the sites. Abundance fluctuations of G. omega show notable relations to early-middle Pleistocene climate changes; they considerably increase in abundance at the interglacial stages, suggesting warm water preferences. Gephyrocapsa omega temporarily disappears during the glacial MIS 22 and MIS 20. Above MIS 20, an impoverishment in G. omega and in the total abundance of medium-sized gephyrocapsids occurs. A decrease in abundance of G. omega is observed between the western Site 977 and the easternmost Site 967 in the Mediterranean Sea, as a possible response to high salinity and/or low nutrient content. Possible environmental influences on the distribution of R. asanoi and of Reticulofenestra sp. are discussed.

Sapropels in the Mediterranean Sea

Eastern Mediterranean sediments are characterized by cyclic deposition of organic-rich sediments known as sapropels. Enhanced primary productivity combined with bottom water oxygen depletion are thought to be the main drivers for sapropel deposition. We selected sapropel layers from a suite of ODP-Leg 160 cores, and applied a set of geochemical proxies to determine paleo-productivity variations, redox conditions of the water column during deposition, and provenance of detrital material. High sedimentary Ba/Al and Corg contents indicate enhanced primary production, whereas the sedimentary La/Lu ratio, points to an enhanced contribution from a North African riverine source, during sapropel formation. These features are especially pronounced on Sapropels S5 and S7, deposited during a particularly warm climatic interval. This indicates a more intense North African drainage/weathering and consequently run-off for those sapropels that have the most enhanced expression of productivity too. Correspondingly, the latter has also resulted in bottom water redox conditions that have been more severe during these sapropels than during others. Deepwater formation from Adriatic and Aegean areas, thought to be mainly controlled by sustained cooling of preconditioned surface waters, triggers the onset of bottomwater ventilation, thus sapropel duration. Our data, therefore, suggest that the intensity of sapropel formation is determined by the North African monsoonal system, whereas their duration is directed by northern borderlands climatic conditions.