Origin and transformation of organic matter in Pliocene–Pleistocene Mediterranean sapropels: organic geochemical evidence reviewed

Drilling of deep-water post-Messinian sedimentary sequences by ODP Legs 160 and 161 in the Mediterranean Sea has shown that occurrence of organic-carbon-rich sapropels and sapropel-like sediments extends from the Levantine Basin westward into the Alboran Basin. In the eastern Mediterranean, sapropel deposition started in the Early Pliocene, whereas in the Western Basin the onset of sapropel formation occurred later, in the Early Pleistocene. Precessional cycles are apparently the primary external forcing for sapropel formation. Nevertheless, the pattern of sapropel occurrence suggests that the precessional influence is modulated by the glaciation cycles. Large differences were observed in the organic carbon contents of sapropels recovered in the eastern and western Mediterranean. Correspondence between organic carbon contents, Rock-Eval hydrogen index values and elemental C/N ratios indicate that both variations in the production and preservation of marine organic matter have led to the accumulation of high amounts of organic matter in sapropels. Molecular organic geochemical compositions of sapropels from the eastern Mediterranean further confirm that the major fraction of organic matter in sapropels is derived from marine algal sources and has undergone variable oxidation. Enhanced marine productivity and improved preservation of organic matter is central to sapropel formation. Accumulation of increased amounts of land-derived material at times of sapropel formation is also evidenced, supporting the hypothesis of significant periodic freshwater discharges.     

Diagenetic magnetic enhancement of sapropels from the eastern Mediterranean Sea

Diagenetic dissolution of magnetic minerals has been widely observed in organic-rich sediments from many environments. Organic-rich sediments from the eastern Mediterranean Sea (sapropels), recovered during Leg 160 of the Ocean Drilling Program, reveal a surprising catalogue of magnetic properties. Sapropels, from all sites studied across the eastern Mediterranean Sea, are strongly magnetic and the magnetization is directly proportional to the organic carbon content. The magnetization of the sapropels is dominated by a low-coercivity, probably single domain magnetic mineral (with an inverse magnetic fabric) that exhibits a clear decay in magnetic properties when exposed to air. During heating, the magnetic particles irreversibly break down between 360 and 400°C. The contrast between the magnetic properties of sapropels and surrounding sediments is marked, with remanence intensities of sapropels often being more than three orders of magnitude higher than those of underlying sediments. The contrast between the magnetic properties of sapropels and the surrounding sediments is apparently controlled by non-steady-state diagenesis: sulphate-reducing conditions dominated during sapropel deposition, while overlying sediments were deposited under oxic conditions. The mineral responsible for the magnetic properties of sapropels is most likely to have formed under sulphate-reducing conditions that existed during times of sapropel formation. Attempts to identify this mineral have been unsuccessful, but several lines of evidence point toward an unknown ferrimagnetic iron sulphide phase. The influence of diagenesis on the magnetic properties of cyclically-deposited eastern Mediterranean sedimentary sequences suggests that magnetic parameters may be a useful proxy for diagenesis in these sediments.     

Review of recent advances in the interpretation of eastern Mediterranean sapropel S1 from geochemical evidence

The sediments of the eastern Mediterranean basin contain C_org-enriched layers (sapropels) interbedded with the C_org-poor sediments which form by far the greater part of the record. While it is generally appreciated that different surface ocean productivity and bottom water conditions are necessary for the formation and preservation of these two sediment types, less attention has been paid to diagenetic effects which are an expected consequence of transitions between dramatically different bottom water oxygenation levels. A geochemical interpretation has emerged of post-depositional oxidation of the most recent sapropel (S1), initially based on the relationship of the Mn, Fe, C_org and S concentration/depth profiles observed around S1, and the characteristic shapes of these elemental profiles known from other situations. This indicates that post-depositional oxidation has removed approximately half of the visual evidence of the sapropel (∼6 cm from a total of ∼12 cm in the deep basin). The oxidation interpretation from redox-sensitive element redistribution profiles has subsequently been consolidated with evidence from pore water (O₂, NO⁻₃, Mn²⁺ and Fe²⁺) studies, from characteristic solid phase Ba profiles which yield palaeoproductivity records, and from oxidation-sensitive indicator trace elements (I and Se). So far, these geochemical observations have been concentrated in the deeper central parts of the basin, where sediment accumulation rates are lower than on the basin margins, and radiocarbon dating indicates that S1 formation occurred between 5.3 and 9.0 ky (uncorrected conventional radiocarbon time). It remains to be demonstrated whether or not these times are applicable to the entire E. Mediterranean basin. The implications of these findings to guide sampling in future work on the S1 productivity episode and on older sapropels for palaeoenvironmental investigations are discussed.     

Middle Miocene (Langhian) sapropel formation in the easternmost Mediterranean deep-water basin: Evidence from northern Cyprus

Mid-Miocene (Langhian; ∼15.4 Ma) sapropels formed within the easternmost Mediterranean basin, now uplifted in northern Cyprus. These sapropels represent the oldest known sapropels in a predominantly marl succession. Six well-developed sapropels were studied. Strontium isotope dating of twelve samples gave a preferred age of ∼15.4 Ma (Langhian); i.e. during the final phases of the Middle Miocene Climatic Optimum (MCO). The age of the best-preserved nannofossil assemblage (Langhian) is close to the strontium ages. The Langhian strontium ages are preferred over an alternative early Serravallian age for less well-preserved nannofossil assemblages. Total organic carbon contents in the sapropels reach maximum values of 3.9 wt.%. Relative to the host marls, the sapropels show enrichments in terrigenous-derived minerals and related major and trace elements. Sedimentological evidence indicates that the terrigenous sediments were eroded from the northern borderlands of the deep-water basin under warm, humid conditions. High fresh-water run-off from surrounding landmasses is likely to have promoted a low-salinity lid to the eastern Mediterranean deep-water basin. This, in turn, would have restricted deep-water ventilation and promoted widespread anoxia. Exceptionally high concentrations of chalcophile elements (e.g. Cu, Ni and Zn) are consistent with anoxic conditions. Abundant nutrient-rich fresh-water input is also likely to have stimulated siliceous productivity (although any siliceous microfossils did not survive diagenesis). A significant role for diagenesis in sapropel formation is indicated by the mobilisation of Ba from sapropels to marl directly beneath. Orbitally induced dry–wet oscillation, the mechanism invoked to explain the Pliocene to Holocene sapropels, apparently was already in place during the latest stages of the MCO when the Langhian sapropels accumulated. These sapropels accumulated immediately after the Middle Miocene closure of the Southern Neotethys when the Eastern Mediterranean Sea apparently became more sensitive to orbital cyclicity. The development of a semi-enclosed deep-water basin was, therefore, a prerequisite for sapropel formation.     

A synthetic pollen record of the eastern Mediterranean sapropels of the last 1 Ma: implications for the time-scale and formation of sapropels

The Quaternary climate of southern Europe (south Italy and Greece) is investigated by pollen analysis of the sapropels which were deposited in the deep eastern Mediterranean Sea during the last 1 million year (Ma). The time-scale of core KC01b in the Ionian Sea has been established by tuning its oxygen isotopic record to the ice volume model of Imbrie and Imbrie (1980). For the last 250,000 year (250 ka), the previous pollen studies and astronomical tuning have been confirmed. Sapropels were deposited under a large range of Mediterranean climates: fully interglacial, fully glacial, and intermediary, as revealed mainly by the balance between the respective pollen abundances of oak (Quercus) and sage-brush (Artemisia). The high value of the oak reveals the warm and wet climate of an Interglacial, and the high value of the sage-brush, the dry and cold climate of a Glacial. Whereas the Mediterranean climate is directly related to the variation of the high-latitude ice sheets, the deposition of sapropels is not so. In contrast with the wide climatic range, sapropels were deposited only when summer insolation in the low latitudes reached its highest peaks. However, between 250 ka and 1 Ma, that stable pattern is not yet established. Only six sapropels are observed, many expected ones do not appear, even as ghosts signalled by peaks of barium abundance, that remain after the post-deposition oxidation of organic matter. The pattern of sapropel formation in stable and direct relationship to highest insolation does not seem to apply. For five of those sapropels, neither climate extremes are observed; they mainly formed during intermediary types of Mediterranean climate. In contrast, one sapropel (and one ghost) relates to a relatively low peak of insolation, and its climate is of a unique, composite type not seen later. This might suggest an unsuspected, more complex pattern linking the formation of Mediterranean sapropels to the astronomical configuration.     

The occurrence and significance of Pleistocene and Upper Pliocene sapropels in the Tyrrhenian Sea

Numerous sapropels and sapropelic strata from Upper Pliocene and Pleistocene hemipelagic sediments of the Tyrrhenian Sea show that intermittent anoxia, possibly related to strongly increased biological productivity, was not restricted to the eastern Mediterranean basins and may be a basin-wide result of Late Pliocene-Pleistocene climatic variability. Even though the sapropel assemblage of the Tyrrhenian Sea clearly originates from multiple processes such as deposition under anoxic conditions or during spikes in surface water productivity and lateral transport of organic-rich suspensates, many “pelagic sapropels” have been recognized. Stratigraphic ages calculated for the organic-rich strata recovered during ODP Leg 107 indicate that the frequency of sapropel formation increased from the lowermost Pleistocene to the base of the Jaramillo magnetic event, coinciding with a period when stable isotope records of planktonic foraminifera indicate the onset of climatic cooling in the Mediterranean. A second, very pronounced peak in sapropel formation occurred in the Middle to Late Pleistocene (0.73-0.26 Ma). Formainifers studied in three high-resolution sample sets suggest that changes in surface-water temperature may have been responsible for establishing anoxic conditions, while salinity differences were not noted in the faunal assemblage. However, comparison of sapropel occurrence at Site 653 with the oxygen isotopic record of planktonic foraminifers established by Thunell et al. (Proc. ODP, Sci. Results 107, 1990) indicates that sapropel occurrences coincide with negative δ¹⁸O excursions in planktonic foraminifers in thirteen of eighteen sapropels recognized in Hole 653A. A variant of the meltwater hypothesis accepted for sapropel formation in the Late Pleistocene eastern Mediterranean may thus be the cause of several “anoxic events” in the Tyrrhenian as well. Model calculations indicate that the amount of oxygen advection from Western Mediterranean Deep Water exerts the dominant control on the oxygen content in deep water of the Tyrrhenian Sea. Inhibition of deep-water formation in the northern Adriatic and the Balearic Basin by increased meltwater discharge and changing storm patterns during climatic amelioration may thus be responsible for sapropel formation in the Tyrrhenian Sea.     

Modes of sapropel formation in the eastern Mediterranean: some constraints based on pyrite properties

Pyrite formation within and directly below sapropels in the eastern Mediterranean was governed by the relative rates of sulphide production and Fe liberation and supply to the organic-rich layers. At times of relatively high SO²⁻₄ reduction, sulphide could diffuse downward from the sapropel and formed pyrite in underlying sediments. The sources of Fe for pyrite formation comprised detrital Fe and diagenetically liberated Fe(II) from sapropel-underlying sediments. In organic-rich sapropels, input of Fe from the water column via Fe sulphide formation in the water may have been important as well. Rapid pyrite formation at high saturation levels resulted in the formation of framboidal pyrite within the sapropels, whereas below the sapropels slow euhedral pyrite formation at low saturation levels occurred. δ³⁴S values of pyrite are −33‰ to −50‰. Below the sapropels δ³⁴S is lower than within the sapropels, as a result of increased sulphide re-oxidation at times of relatively high sulphide production and concentration when sulphide could escape from the sediment. The percentage of initially formed sulphide that was re-oxidized was estimated from organic carbon fluxes and burial efficiencies in the sediment. It ranges from 34% to 80%, varying significantly between sapropels. Increased palaeoproductivity as well as enhanced preservation contributed to magnified accumulation of organic matter in sapropels.     

Benthic foraminiferal successions across Late Quaternary Mediterranean sapropels

Benthic foraminiferal records across Late Quaternary Mediterranean sapropels S6, S5 and S1 are reviewed and re-considered in the light of recent advances in foraminiferal ecology. It is suggested that the main factor controlling the foraminiferal successions that occur immediately before and after sapropel deposition is the amount of time involved in the onset of anoxic conditions and in the re-oxygenation of the benthic environment. Faunas dominated by deep infaunal taxa such as Globobulimina and Chilostomella reflect a very gradual decrease or increase of bottom water oxygenation. Post-sapropel faunas dominated by small biconvex, trochospiral taxa, which are inferred to have a much more opportunistic life strategy, are typical of a very rapid re-oxygenation of the benthic environment after sapropel deposition. The time involved in re-oxygenation depends upon the mechanism causing sapropel formation. The faunal succession found above sapropel S5 suggests a basin with a strong density gradient in the upper part of the water column during sapropel deposition, followed by a rapid turnover of the following column and quick re-oxygenation of the benthic environment. In contrast, the faunal succession above sapropel S6 suggests a water column with a more gradual density gradient deeper in the basin, a progressive deepening of the halocline, and a very slow increase of bottom water oxygenation.     

Eastern Mediterranean sapropel S1 interruption: an expression of the onset of climatic deterioration around 7 ka BP

We discuss the palaeoclimatic interpretation of unprecedented high-resolution micropalaeontological studies of short-term (2 to 4 centuries) interruptions within early Holocene organic-rich layer (sapropel) S1 from the eastern Mediterranean. Results for cores from the Adriatic and Aegean seas that contain `double' S1 sapropels indicate that these interruptions, which are centred roughly around 7000 years <sup>14</sup>C<sub>nc</sub> BP, are genuine and related to climatic deterioration. This interpretation is endorsed by a coeval dry event recorded in terrestrial records and indications of climatic deterioration affecting human migration patterns and early societies in Egypt. The presence of sapropel interruptions in the two major source areas of deep water for the entire eastern Mediterranean likely implies that similar intervals may be found throughout the basin, provided that sedimentation rates and sampling resolutions allow the detection of events with a duration of only several centuries. Moreover, our results show that the `sapropel mode' of circulation comprises a delicate balance between reduced ventilation and enhanced productivity, which is easily disturbed through surface water cooling triggering a short time of improved deep water ventilation.     

Sedimentology and geochemistry of an exceptionally preserved last interglacial sapropel S5 in the Levantine Basin (Mediterranean Sea)

A combined study of lithological, geochemical and physical sediment properties is reported from a completely laminated S5 sapropel, recovered in three gravity cores (M40-4 SL67, M51-3 SL103, M51-3 SL104) from the Pliny Trench region of the eastern Mediterranean. The thickness of the studied sapropel S5 varies between 85 and 91 cm and tops most S5-sapropels in the Mediterranean. Based on optical features like color and thickness of laminae, the sapropels were subdivided into thirteen distinct lithostratigraphic zones. These zones, as well as the finer layering pattern within them, could be followed exactly among the three cores, indicating that the processes responsible for this variation acted at least on a regional scale. The sapropel sediment is characterized by exceptionally high porosity, which is strongly correlated with Si/Ca. This relationship implies that the sapropel is in essence an organic-matter rich diatomite and its exceptional thickness can be explained by preservation of diatoms forming a loosely packed sediment fabric. Compared to other S5 sapropels, the preservation of diatoms has apparently led to a twofold increase in the thickness of the sapropel layer. Relative abundances of 10 elements were determined at ultra-high resolution (0.2 mm) by XRF-scanner over the complete length of each sapropel including several cm of enclosing marl. An analysis of the chemical data indicates that the lowermost 13 cm of the sapropel is chemically more similar to the underlying marl and that the sediment chemistry shows different signals at different scales. The strongest pattern is the contrast between the sapropel and the surrounding marl, which is accentuated in elements indicative for redox conditions as well as terrigenous sediment input and productivity. Within the sapropel, a mm- to cm-scale layering is observed. The abundances of many elements are systematically linked to the pattern of these layers, indicating a common origin, related to productivity and/or terrigenous sediment and/or redox conditions. This pattern indicates a link to a regional climatic process, making the S5 sapropel horizon in M40-4 SL67, M51-3 SL103 and M51-3 SL104 a potential high-resolution archive of climatic variability during the last interglacial in the Mediterranean Sea and its adjacent landmasses.     

Deposition of sapropel S1 sediments in oxic pelagic and anoxic brine environments in the eastern Mediterranean: differences in diagenesis and preservation

Sediments from a boxcore in the previously anoxic brine-filled Poseidon Basin, eastern Mediterranean, have been studied and compared to sediments deposited in a `normal' eastern Mediterranean environment. The boxcore can be divided into three main sedimentary intervals based on AMS-radiocarbon ages, foraminiferal and geochemical zonations. From the base of the core upwards these are: (1) 12.3–31.2 cm, organic-rich sediments redeposited from within the brine; (2) 6.6–12.3 cm, sediment containing a `cold' foraminifera fauna redeposited from above the brine into the basin while the brine was still present; (3) 0–6.6 cm, oxic pelagic sediment accumulated since the reoxygenation of Poseidon Basin which occurred ∼1800 yrs BP. Near the base of the latter unit, a Mn-oxide peak has formed and it marks the present boundary between oxic and suboxic environments. A progressive downward oxidation front, which is usually found in `normal' sapropel S1 sediments, has never formed in Poseidon Basin sediments. This has resulted in the preservation of the relationship between organic carbon and organic-related trace elements, e.g. Se, in the organic-rich sediments of Poseidon Basin, whereas such a relationship has been obliterated in `normal' sapropel S1 sediments. On the basis of the carbonate content as well as the Sr/Ca ratio, preservation of carbonates appears to be better in the brine sapropel sediments of BC15 than it is in `normal' sapropel S1 sediments. The high opal content of BC15 shows that biogenic opal is also much better preserved. The overall lower C<sub>org</sub>/Ba ratio in BC15 suggests a better preservation of barite relative to that of organic carbon in shallow brine sediments, but is as yet inconclusive for the organic carbon preservation potential of brine relative to `normal' unoxidised sediments.     

Origin and differentiation of clay minerals in pelagic sediments and sapropels of the Bannock Basin (Eastern Mediterranean)

Two cores from an anoxic basin of the southeastern Mediterranean Ridge were investigated to compare the clay mineralogy of pelagic sediments and of the interbedded sapropels. The sediments of Core BAN 84-02, raised from the basin floor, and those of Core BAN 84-08, from the eastern plateau of the Bannock Basin, provide evidence for different sedimentary environments. The anoxic conditions, which are still present near the bottom, produce an important decrease in smectite crystallinity (Core 02), whereas well-organized smectite persists in the normally oxygenated sediments (Core 08). Detrital clay minerals from various sources were deposited in the basin and no appreciable diagenesis was recognized downcore.

The clay mineralogy of the sapropels shows remarkable differences compared to the pelagic sediments. The changes observed are dependent on aggressive chemical reaction and on the sudden input of detrital crystalline sediments into the stagnant environment. A climatic curve registers the variable degree of clay mineral hydrolysis in continental areas and exhibits good correspondence with an already published oxygen isotope curve for the area.     

Mediterranean functioning and sapropel formation: respective influences of climate and hydrological changes in the Atlantic and the Mediterranean

During Ocean Drilling Program (ODP) Legs 160 and 161, sapropels were recovered both in the western and eastern Mediterranean. This obliges to a reassessment of the previous studies focused on sapropels from only the eastern Mediterranean, and to consider the changes which occurred in the Mediterranean climate but also in the water characteristics both in the Atlantic and in the western Mediterranean. In the North Atlantic, the position of the polar front which migrated southwards during glacial times and the melting of northern ice caps during interglacial periods, together with the convection in the Labrador and Norwegian Seas, appear essential to control the salinities of the waters facing the Strait of Gibraltar. The salinities of the surface and intermediate layers constitute the first driving force of the Mediterranean dynamics, the second driving force being the Mediterranean climate. The stagnation of deep waters leading to sapropel deposition in the western Mediterranean may be explained by a drastic weakening of the density difference between Mediterranean outflow and Atlantic intermediate waters facing the Strait of Gibraltar. This weakening was induced primarily by the salinity decrease of Atlantic surface water and secondly by a rather high salinity in the Atlantic intermediate layer, rather than by a drastic deterioration of the Mediterranean climate. This scenario probably concerns most of the sapropel events and it may be used for the knowledge of Atlantic and Mediterranean functioning over climatic changes.     

Carbon and nitrogen isotope excursions in mid-Pleistocene sapropels from the Tyrrhenian Basin: Evidence for climate-induced increases in microbial primary production

The modern Mediterranean Sea is oligotrophic, yet its sediment record contains layers of organic-carbon-rich sapropels at 21 ky (precessional) spacing that imply periods of elevated paleoproductivity that approached the high productivities of modern upwelling systems. Resolution to this paradox is provided by lines of evidence suggesting that the mode of primary productivity changed from one dominated by algae to one during times of sapropel deposition in which photosynthetic bacteria were important. We have made a high-resolution comparison of the organic carbon and nitrogen isotopic compositions of three sapropels and their background sediments in a 3-m sequence that corresponds to 1001 to 946 ka. Organic δ¹³C values systematically increase from − 26‰ to − 21‰ and δ¹⁵N values systematically decrease from 4‰ to < 0‰ as organic carbon mass accumulation rates increase in the sapropel layers. The increase in carbon isotope values mirrors the increases in primary productivity and associated organic matter export indicated by the increased mass accumulation rates. The decrease in nitrogen isotope values implies major contributions of nitrogen-fixing cyanobacteria to the total marine productivity. The precessional minima with which sapropels coincide were times of wetter climate that stratified the surface Mediterranean Sea, increased delivery of soil-derived phosphorus, and evidently amplified microbial primary production. Our high-resolution study reveals several relatively rapid excursions into and out of the high-productivity mode that suggest that sapropel deposition was a climate-sensitive surface-driven phenomenon that was not accompanied by basin-wide stagnation.     

Cyclic variations in the chemical composition of eastern Mediterranean Pliocene sediments: a key for understanding sapropel formation

Two Pliocene Mediterranean sediment cores from Ocean Drilling Program (ODP) Leg 160, Sites 964 (Pisano Plateau, Ionian Basin) and 967 (lower northern slope of Eratosthenes Seamount, south of Cyprus) have been analyzed for major and minor elements (Si, Ti, Al, Fe, Mg, Ca, K, Ba, Cr, Ni, V, Zn, Zr) by X-ray fluorescence analysis at a depth resolution of 3 to 4 cm (a total of 430 samples). Core 964C-9H comprises five sapropels with up to 9.7% total organic-carbon (TOC), one 2.5-m-thick turbidite, and a 50-cm segment of a second turbidite, whereas Core 967B-9H contains eight sapropels with TOC contents of up to 6.7%. Cyclic variations in carbonate content and detrital-matter composition are evident at both sites. At Site 964 (Pisano Plateau) terrigenous detrital-matter chemistry reflects periods of stronger Saharan dust input (higher Si/Al and Zr/Al ratios) alternating with fluvial input from the northern borderlands (higher Mg/Al ratios). Cyclicity is not well-expressed at this location because turbidites and winnowing occur. Site 967 (Eratosthenes Seamount) sediments are strongly influenced by discharge from the Nile River during humid periods (low K/Al and Mg/Al ratios). At Site 967 sapropels occur only during periods of enhanced Nile discharge with correspondingly lower Si/Al, Ti/Al, Mg/Al, K/Al, and Zr/Al ratios. Accumulation rates of carbonate and terrigenous detrital matter were 30% lower during such episodes because of the reduction in eolian input and carbonate production and/or carbonate dissolution. Periodical Ba enrichments, which are not only seen in the sapropels, but in every K/Al minimum, document the association of enhanced bioproductivity and sapropel formation. As calculated from excess Ba concentrations, productivity increased by up to a factor of five during intervals of intensified Nile runoff. Fluviatile discharge seems to be responsible for an enhanced input of nutrients and suspended matter containing low Mg/Al and K/Al ratios. Based on organic-carbon concentrations, episodes of sapropel formation lasted at least from 1000 to 4000 years at Site 964, and from 2000 to 6000 years at Site 967. Periods of enhanced bio-productivity, as defined by Ba enrichments, lasted from 8000 to 12,000 years at Site 967. Episodes of high river discharge and corresponding nutrient input, as well as conditions of sapropel formation, seem to have lasted longer in the eastern part of the basin (Site 967) than at the Pisano Plateau (Site 964).     

Messinian pre-evaporite sapropels and precession-induced oscillations in western Mediterranean climate

Cyclical fluctuations in planktic foraminiferal assemblages have been recognized in the pre-evaporitic Messinian in a marginal basin of the western Mediterranean. The fluctuations coincide with a dominantly precession-controlled sedimentary cyclicity (sapropels). During sapropel deposition, high planktic foraminiferal diversities are indicative of relatively stable marine conditions, while during homogeneous marl deposition low diversities seem to indicate the presence of unfavourable, more saline surface water conditions. The dominance of a precession-related signal indicates that regional climate oscillations rather than (obliquity-related) glacio-eustatically controlled influxes of Atlantic and/or Mediterranean waters are responsible for the faunal fluctuations and sedimentary cyclicity. Our scenario links the persistence of normal marine conditions during sapropel formation with increased rainfall and run-off along the western Mediterranean at times that perihelion occurred in Northern Hemisphere summer. Less favourable, highly saline surface water conditions prevailed during periods of drier climate induced by opposite precessional extremes. The cyclical oceanographic fluctuations could also have governed periodic reef growth along the margins.     

Evidence for the evolution of an oxygen minimum layer at the beginning of S-1 sapropel deposition in the eastern Mediterranean

The sediments of the eastern Mediterranean basin contain a series of organic-rich sapropels intercalated with organic-poor nannofossil oozes. Until recently the timing of the onset of sapropel formation was not known accurately because of the low resolution achievable by conventional radiocarbon dating. Compilation of all available ¹⁴C-AMS dates show that the base of S-1 (the most recent sapropel) was initiated 8800 years B.P. (¹⁴C age corrected by 400 years for reservoir effect) under a 500 m water column and moved progressively into deeper water reaching depths of 3500 m at 8200 years B.P. The linear correlation between the age of S-1 onset and water depth

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suggests that formation of sapropels moved into deeper water at a rate of 1000 m/200 year. A model is suggested in which export production which sank below the well-mixed surface layers (500 m) was respired consuming dissolved oxygen in the Levantine deep water until a threshold value was reached when sapropels began to be preserved in the sediment. This resulted in a progressively deepening oxygen minimum zone with time until eventually the entire deep water in the basin was oxygen depleted. Assuming that the threshold value for sapropel formation was complete anoxia, it was calculated that primary productivity in the basin during the deposition of S-1 was a factor of 5 greater than that found at present.     

Geochemistry of eastern Mediterranean sediments: Primary sediment composition and diagenetic alterations

Two cores recovered in the eastern Mediterranean were analysed for major, minor and trace elements. The primary chemical composition of the sediment is different at each location, probably because the lithological sources and the relative biogenic contributions differ.

Carbonates are important for the concentration of Ca, Mg and Sr, whereas aluminosilicates determine the concentration of Si, Al, K, Li, Y and Be, and to a lesser extent that of Fe, Cr, Ti, Mg, Zn and Zr. In sapropels, organic carbon and sulphur seem to be closely related. Bromine, Mo, P, Fe, V, Cu, Zn, Co, Ni and Cr are closely associated with organic and sulphidic compounds. The concentration versus depth profile for organic carbon in two sapropels points to a rapid establishment of conditions that gave rise to sapropel formation, followed by a gradual transition back to “normal” conditions.

The primary composition is overprinted by diagenetic processes. Sulphate-reducing conditions occurred during and just after sapropel deposition. A progressive oxidation front mechanism, which became active after sapropel deposition, is responsible for additional major geochemical changes. This diagenetic phenomenon has strong implications for the chemistry of Fe, Mn, Ni, Co, Zn, Cu, Cr, V, U, As and Sb.     

The Nile Cone: Submarine fan development by cyclic sedimentation

The Quaternary sections of the Nile Cone in the eastern Mediterranean are formed by regionally extensive repetitions of sediment sequences (cyclothems s.l.) showing a successive, orderly arrangement of sediment types. Detailed lithofacies analysis reveals the recurrence of three basic terms in many cores: a basal olive-gray hemipelagic mud and turbidite sequence; a middle sapropel sequence; and an upper yellowish-orange hemipelagic sequence, including calcareous ooze, and a turbiditic sequence. This cyclic sedimentation closely reflects the Quaternary dynamics. The development of the Nile submarine fan in an enclosed, silled basin has resulted in a particularly close relation between biogenic-terrigenous depositional patterns and climatic and oceanographic factors affecting the Mediterranean.     

Palaeoproductivity and post-depositional aerobic organic matter decay reflected by dinoflagellate cyst assemblages of the Eastern Mediterranean S1 sapropel

In the reconstruction of bioproductivity in surface waters the extent to which a proxy has been diagenetically altered is often a matter of debate. Here we investigate how organic- and calcareous-walled dinoflagellate cysts can be used for separately estimating bioproductivity and oxygen related diagenesis. This is achieved by studying the cyst content of the most recent Eastern Mediterranean sapropel S1, that is thought to have been deposited under conditions of increased primary production in surface waters and possible anoxia in the bottom waters. Based on chemical evidence, it has been shown that the visible sapropelic layer represents only the residual lower part of what was initially a much thicker sapropel, as a result of post-depositional decay of organic matter related to oxygen penetration into the sediments. The effect of aerobic organic matter decay on the cyst associations is studied through the comparison of the unaffected, lower part of the initial sapropel and the ‘oxidised’ upper part. Comparing the unaffected sapropelic sediments with pre- and post-sapropelic material gives insight into the relationship between fossil cysts assemblages and palaeoproductivity.Impagidinium aculeatum, Impagidinium patulum, Operculodinium israelianum, Polysphaeridium zoharyi and probably Impagidinium spp., Impagidinium paradoxum and Nematosphaeropsis labyrinthus are very resistant against aerobic decay and their accumulation rates appear to be primarily related to productivity in surface waters. Protoperidinium and Echinidinium species, on the other hand, are shown to be very sensitive and can be used to recognise oxygen-related decay. The calcareous-walled dinoflagellate cysts seem to be unaffected by oxic organic matter decay in Mediterranean sediments.