Organic geochemical and palynological evidence for terrigenous origin of the organic matter in Aegean Sea sapropel S1

Organic geochemistry and micropaleontology are used to determine the origin of sapropel S1 in the Aegean Sea. Low-molecular-weight (C₁₅, C₁₇ and C₁₉) n-alkane data show that net primary productivity (NPP) increased from ∼14,000 to 10,000 yr BP at the glacial interglacial transition, but the onset of S1 at 9600 yr BP marks a sharp decline in NPP, which remained low until ∼8200 yr BP. The start of sapropel deposition is marked by increased total organic carbon (TOC) and pollen-spore concentrations, together with increased high-molecular-weight (C₂₇, C₂₉, C₃₁ and C₃₃) n-alkanes. Pollen assemblages show large influx of tree pollen from central-northern European forests. Increases in high-molecular-weight n-alkanes suggest greater influx of fresh vascular plant material at the start of S1, although the amount is small compared to other insoluble organic matter. Palynological studies showed that most of this insoluble organic matter are flocks of dark-brown amorphous kerogen, typical of terrigenous humic compounds. From ∼8200 yr BP to the top of S1 at ∼6400 yr BP, there is a decline in high-molecular-weight n-alkanes and terrigenous kerogen, and an increase in low-molecular-weight n-alkanes, suggesting that NPP recovered during the later deposition of S1 in the Aegean Sea. The increase in low-molecular-weight n-alkanes coincides with the recovery of coccolithophores and dinoflagellates, suggesting that these phytoplankton are primarily responsible for the low-molecular-weight n-alkane variations. These data from the Aegean Sea support the model for sapropel deposition resulting from increased influx of TOC during times of stagnant bottom water, but disagree with Mediterranean models prescribing a large increase in marine productivity.     

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.     

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.     

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.     

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).     

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.     

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.     

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.     

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.     

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.     

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.     

Age,regional variation,and shallowest occurrence of S1 sapropel in the northern Aegean Sea

Thirteen gravity cores taken off northern Greece contain the S1 sapropel, as a single layer in cores from water depths <250 m and usually as a double layer in cores from deeper water. Total thickness of the sapropel layer is proportional to thickness of sediment between the sapropel and an 18 ka seismic marker. These observations suggest that the sapropel is not diachronous. Five AMS radiocarbon dates of molluscs and echinoderms indicate an age of 6.4–9.2 ka for the S1 sapropel, considerably younger than previous age estimates in the northern Aegean Sea of 9–13 ka, which were based on bulk sample dating techniques.     

Possible diagenetic mobilization of barium in sapropelic sediment from the eastern Mediterranean

In the last few years it has frequently been suggested that Ba is a useful indicator of paleoproductivity. The formation of some sapropels in the Eastern Mediterranean is considered to be related to, or to coincide with, periods of enhanced productivity. A high-resolution sampling study has been undertaken in order to investigate whether the Ba distribution in sapropels reflects a primary input signal or whether it has been altered by diagenetic processes.

On the basis of our results we suggest that three diagenetic stages determine the distribution of Ba. During deposition of the sapropel (stage 1) Ba is mobilized as anoxic conditions prograde. After deposition of the sapropel (stage 2), a progressive oxidation front develops. This front induces the formation of Mn and Fe enrichments and barite precipitation at the oxic/anoxic boundary. Barite precipitation is believed to be caused mainly by a rise in the porewater sulphate concentration after sulphides have been oxidized by the front.

Upon burial (stage 3), suboxic conditions develop as the oxygen becomes exhausted again. In contrast to Fe- and Mn-oxyhydroxides which dissolve and reprecipitate at higher levels, barite is preserved because dissolved sulphate is not depleted.

The interpretation of the Ba distribution in organic-rich sediment is not straightforward. Diagenetic reallocation of a primary Ba signal will possibly disturb the relationship between Ba and organic production. Consequently, one must be very cautious when invoking Ba as a paleoproductivity indicator.     

Soil-sized eolian dusts from the lower troposphere of the eastern Mediterranean Sea

Soil-sized eolian dusts have been collected by a mesh technique from the lower troposphere of the eastern Mediterranean. The overall average dust-loading in this region is 14 μg m^?3 of air, which is among the highest recorded for maritime soil-sized dusts.There are two distinct dust populations in the eastern Mediterranean; these have been termed the “northeastern Mediterranean assemblage” and the “southeastern Mediterranean assemblage”.The dusts of the “northeastern assemblage” originate in the soils of southern Europe. The average dust-loading of this assemblage is 12 μg m^?3 of air, and illite is the principal clay mineral with secondary amounts of kaolinite and the smectites. These dusts make only a secondary contribution to the land-derived material in the underlying deep-sea sediments.The dusts of the “southeastern assemblage” have their origin in the desert belts of North Africa and the Middle East. Their average dust-loading is 17 μg m^?3 of air, and kaolinite is their dominant clay mineral. Dusts of the “southeastern assemblage” make an important contribution to the land-derived fractions of some eastern Mediterranean deep-sea sediments.In addition to eolian dusts, river-transported material from the island of Cyprus has also been investigated. The effects of this “Cyprus assemblage” on sedimentation in the eastern Mediterranean is confined to the immediate vicinity of the island itself.     

Seamont magnetism in the Ionian Sea,eastern Mediterranean

Several seamounts in the Ionian Sea, the largest unit in the eastern Mediterranean, have magnetic anomalies. The magnetization vectors of six of these seamounts have been calculated. These paleomagnetic data suggest that the Ionian Sea is composed of several crustal units which came to their present location from different directions. This implies that there has been relative motion in the past between various land masses around the Ionian Sea. The possibility that the Ionian Sea is composed of several crustal units is supported by observations of the magnetic field over the area which is of different character in the north and south. The major limitation in applying the paleomagnetic data into an evolutionary scheme is that all the seamounts in the Ionian Sea as well as its crust are undated.     

Anoxic basins of the eastern Mediterranean: geological framework

A brief review of the geological knowledge on the anoxic basins of the eastern Mediterranean is presented. Anoxic basins have been discovered in two different geological settings in the eastern Mediterranean. Bannock Basin belongs to the compressional style of the Mediterranean Ridge, and Tyro and Poseidon Basins belong to the transcurrent tectonic style of the Strabo Trench. The origin of the basins is subsurface salt dissolution triggered by tectonic deformation of the sediments on the Mediterranean Ridge, and tectonic subsidence (pull-apart mechanism) in the Strabo Trench. The onset of a deep-sea brine lake is always related to the outcrop of Messinian salts on the side-walls of the basin. The rate of basin subsidence controls the evolution of the brine lakes, which can also be completely diluted by bottom water circulation.     

Tectonic elements and crust of the eastern Mediterranean Sea

Seismic reflection and gravity data show the eastern Mediterranean Sea to be evolving into several basins as a result of differential vertical movements. The Levantine Basin and deeper Herodotus Basin are separated by a buried ridge (horst? or faulted geanticline?) lying west of Eratosthenes Seamount, which in turn is the more elevated part of a northeast-trending geanticline truncated along its eastern flank by a graben. To the east, gravity trends in the Levantine Basin are parallel to the graben. These features and trends are similar to those seen on land in Egypt and the Levant and imply continuity of structure offshore. Combined with other geological and geophysical information the observations suggest that the eastern Mediterranean crust is the marginal extension of the African continental crust. Although the character of the Florence Rise and Anaximander Mountains, the northward tilting and subsidence of the Antalya and Finike Basins, and the apparent continuation of the Strabo Trench south of the Florence Rise suggest underthrusting of the Turkish plate by Africa, there may be insufficient seismicity. There is no active volcanic arc, and the trench is too poorly developed to confirm active subduction as the sole manifestation of plate convergence. Normal subduction probably ended within the past 5 m.y. with the disappearance of all oceanic crust between Turkey and Africa. Plate convergence continues with only limited underthrusting of Africa along the Cypriot Arc, but with regional deformation along zones of weakness within a wide (300 km?) band stretching from the Herodotus Basin to the east along the northern edge of the African and Arabian plates.