Geochemistry of eastern Mediterranean sedimentary cycles : on the origin of Miocene to Pleistocene sapropels, laminites and diatomites

Abstract

A brief history of sapropels The word "sapropel" first appears in the literature in 1904, when Potonié mentions that Prof. Dr. Schulze suggested that this word should be used as the international scientific term for Faulschlamm [Potonié, 1904]. Sapropel is a contraction of the literal translation of the German words Fäulniss and Schlamm into ancient Greek (F"BD`H and B08`H, meaning putrefaction and mud). Potonié uses the term to describe a dark-coloured sediment, containing decomposing organisms, deposited under stagnant water. Fossil sapropel deposits are subsequently named sapropelites [Twenhofel, 1926]. These terms are commonly used for organic-rich lake sediments or certain oil source rocks, but were introduced to marine geosciences by Olausson who uses the description "sapropelitic mud" for marine sediments containing more than 2% organic carbon [Olausson, 1954]. Without calling them sapropels, Bradley [1938] predicts the occurrence of laminated, organic-rich layers in the Mediterranean, especially in the eastern basin. Kullenberg [1952] first discovered such layers in cores recovered from the Mediterranean seafloor during the 1947- 1948 Swedish deep-sea expedition. These layers might have simply been called black shales, if it were not for Olausson [1961] describing them as "sapropelic layers". Many more organic-rich layers were recovered during Deep Sea Drilling Program (DSDP) Legs 13A (1970) and 42A (1975). Examination of these sediments resulted in an official sapropel definition: "a discrete layer, greater than 1 cm in thickness, set in open marine pelagic conditions, and containing greater than 2.0% organic carbon by weight" [Kidd et al., 1978]. The term sapropelic layer was downgraded and since then designates a layer containing between 0.5% and 2.0% organic carbon. On the origin of sapropels Especially in the decennia since 1970, numerous researchers have studied the sedimentology, palynology, micropalaeontology and geochemistry of Mediterranean sapropels. The aim of these studies: to reconstruct the climatic conditions and hydrographic regime that resulted in sapropel formation. Currently, the Mediterranean (Fig. 1.1) is a land-locked basin separated from the Atlantic Ocean by the shallow Strait of Gibraltar (284 m deep). Ocean surface water flows eastwards into the Mediterranean, becoming denser as a result of evaporation. Between Sicily and Tunisia, water flows through the shallow Strait of Sicily (330 m deep), which?Chapter 1 10 Figure 1.1 Map of the Mediterranean area. separates the western from the eastern Mediterranean. Continuing evaporation finally makes the surface water so saline and dense that it sinks near Cyprus, where it starts its way back to the Atlantic Ocean as Mediterranean Intermediate Water. This anti-estuarine circulation pattern makes the Mediterranean a nutrient desert: it receives nutrient-depleted surface waters and exports its nutrients received by rivers to the Atlantic with its deep water. The same is true for the eastern basin with respect to the western basin, making the eastern Mediterranean a "nutrient desert within a nutrient desert". Present-day low surface water nutrient levels and oxic bottom waters result in deposition of organic-poor sediments (<0.5% organic carbon). For the deposition of organic-rich sapropels, major changes in this system are clearly necessary. At first, the occurrence of organic-rich layers in Mediterranean sediments was reported to be linked to improved preservation of organic matter under anoxic bottom water conditions. Anoxia would result from density stratification of the water column, limiting circulation and supply of oxygen to deep water [Bradley, 1938; Olausson, 1961]. In a key paper, Rossignol-Strick et al. [1982] correlate the most recent sapropel to a period of heavy precipitation in Africa (late Glacial - early Holocene). They concluded that increased Nile outflow produced a low-salinity layer in the eastern Mediterranean, which stratified the water column, culminating in stagnant (anoxic) bottom waters and sapropel formation. A more extreme theory is that increased Nile outflow did not lead to stagnation, but to a reversal of circulation in the eastern Mediterranean from anti-estuarine to estuarine [Calvert, 1983; Sarmiento et al., 1988]. The simple link between sapropel formation and anoxia was challenged by Calvert, who suggested increased surface?Introduction and summary 11 water productivity as an alternative mechanism for sapropel formation [Calvert, 1983; Calvert et al., 1992]. In his view, organic carbon contents of some Mediterranean sapropels were too high to be achieved with present-day productivity even under anoxic bottom water conditions. On the other hand, high productivity in the Mediterranean cannot be achieved with the present-day hydrography. Calvert [1983] invoked the circulation reversal scenario to solve this problem, since with an estuarine circulation the eastern Mediterranean would be a nutrient trap. Alternatively, Rohling and Gieskes [1989] suggested that increased river water input might lead to a shoaling of the density gradient (pycnocline) into the photic zone. This would result in nutrients of intermediate waters becoming available for primary productivity in a so-called "Deep Chlorophyll Maximum". The "productivity versus preservation" debate is still continuing. De revolutionibus orbium coelestium Due to the collision of Africa with Europe, some sediments deposited on the Mediterranean seafloor have been uplifted above sea level. In these land sections, mainly in Greece and Italy, layers enriched in organic carbon are also found. "Real" sapropels are uncommon in those sections, because organic carbon levels of more than 2% are rarely attained. Corresponding horizons in carbonate cycles in the Sicilian Trubi, Narbone and Agrigento formations are simply called "grey layers", after their colour. Organic-rich layers in the famous Vrica section are called laminites. All these dark-coloured layers are repeated monotonously and regularly in the sedimentary record. This suggests that they are part of "Milankovitch cycles", linked to the Earth's orbital cycles of eccentricity, obliquity and precession. Eccentricity is a measure of the ellipticity of the shape of the Earth's orbit around the sun, and varies in main periods of 100,000 and 400,000 years. Obliquity is the variation in the angle of the Earth's axis, which has a main period of 41,000 years. Precession describes the movement of this axis around the surface of a cone, completing a full circle every 26,000 years. These variations affect the global, seasonal and latitudinal distribution of solar insolation on Earth and, therefore, result in climatic fluctuations. The correlation of the cyclic occurrence of sapropels in the Mediterranean to these orbital variations is mainly the result of the efforts of Hilgen and coworkers [Hilgen, 1991a, b; Hilgen et al., 1995]. They developed a continuous record of sapropel occurrences down into the Miocene, and correlated each sapropel to a precession cycle. Sapropel deposition occurs during precession minima, when the Northern Hemisphere receives maximum summer insolation, and climate in the Mediterranean region is relatively wet. The correlation of sapropels to the insolation record is of great significance, because it allows accurate age determination, estimation of sedimentation rates, and comparison of individual sapropels in different settings. Geochemistry of eastern Mediterranean sedimentary cycles The majority of geochemical studies on sapropels focus on Recent sediments recovered from?Chapter 1 12 the Mediterranean seafloor by traditional coring techniques. Sediments up to 1 million years old can be obtained in this way. For the study of older sapropels, samples have to be obtained either from land sections, or by seafloor drilling techniques. In the first part of this thesis ("The Miocene"), the geochemistry, micropalaeontology and sedimentology of 7 to 10 million-year-old sapropels from Crete and Gavdos (Greece) are discussed. It has been suggested that formation of such old sapropels did not result from climatic changes caused by the precession, but rather from an overall warm climate [Cita and Grignani, 1982; Thunell et al., 1984]. However, the characteristics of these Miocene sapropels are very comparable to those of Pliocene and Pleistocene sapropels. Therefore, sapropel formation during the last 10 million years must have resulted from one basic mechanism: precession-induced dry-wet oscillations in Mediterranean climate. Pliocene land sections on Sicily are characterized by a striking alternation of grey-white-beige- white coloured sediments. The grey layers are equivalent to sapropels, but contain much less organic carbon. The formation of these carbonate cycles is still not fully understood, but must result from an intricate interplay of the processes of carbonate productivity, dissolution, and dilution by clays. At the Lido Rossello section on Sicily, six laminated intervals, some of which contain diatoms, are intercalated in the normal grey-white-beige-white sediments. In coeval sediments of the nearby Punta di Maiata section, these laminites are absent. In Chapter 4 it is discussed how these laminites may have formed, and how they are related to the carbonate cycles. It was found that they are productivity events, but there are also indications for the presence of a local anoxic basin during their deposition. A unique opportunity to study sapropels older than 1 million years in marine cores instead of in land sections was offered by ODP (Ocean Drilling Program) Legs 160 and 161 in 1995. During these campaigns, hydraulic coring techniques were used to obtain excellent sedimentary records extending down into the Pliocene. Some of the Pliocene sapropels recovered were extremely well developed, having a very dark colour, distinct lamination, and sharp boundaries. In Chapter 5, it is shown that some of these sapropels are extremely rich in organic carbon, trace elements and pyrite, and contain isorenieratene derivatives (biomarkers for photosynthetic green sulphur bacteria). These sapropels must have been formed when the eastern Mediterranean water column was almost completely sulphidic as a result of high productivity. The same sapropels feature in Chapter 6, where a detailed trace element budget of the eastern Mediterranean during their formation is presented. Calculations show that the trace element enrichment is not (solely) the result of diagenesis, and that next to wind, hydrothermal and river input, western Mediterranean seawater is also needed as a trace element source. This indicates that water circulation was not too much restricted during sapropel formation; in fact, it may have been reversed. A very efficient trace element removal mechanism must have been operative, supposedly scavenging by organic matter and sulphides from an almost completely euxinic water column. This mechanism is also operative in the present-day euxinic Black Sea. As such, these Pliocene Mediterranean sapropels are comparable to several worldwide?Introduction and summary 13 occurring black shales, especially those of the Caenomanian-Turonian Boundary Event (CTBE). However, because of the shorter duration of sapropel formation, the ultimate trace element sources are different for the sapropels (seawater) than for those black shales (hydrothermal and fluvial input). In Chapter 7, the geochemical results of all studied ODP sapropels are presented. These (partly coeval) sapropels stem from four different sites that span most of the eastern Mediterranean, and which represent different water depths. Therefore, these data offer unique opportunities to narrow down the possible scenarios for sapropel formation. It is concluded that Pliocene sapropel formation is not the result of either increased productivity or improved preservation, but that both factors must have played a significant role. Possibly, anoxic conditions developed because of high oxygen demands set by decomposing organic matter, making productivity the key factor determining Pliocene sapropel formation. Sedimentation rates were between 30% lower and 50% higher during Pliocene sapropel formation, which lasted between 1,900 and 10,000 years. Nile runoff and nutrient supply is an important factor in sapropel formation, which is reflected in longer sapropel duration in the eastern part of the eastern Mediterranean than in the western part. Because uplifted Mediterranean marine sediments in land sections are older than approximately 1 million years, a direct comparison between sapropels in marine cores with their equivalents in land sections had not been possible before ODP Leg 160. In the third part of this thesis ("The Pleistocene"), a comparison is made between a laminite in the Vrica section (Italy) and the coeval sapropel in ODP Sites 967 and 969. The laminite is quite different from the sapropel: it is much thicker, richer in clays, and poorer in organic carbon. Only a small part of the differences between the land section and the marine cores is the result of uplift, weathering and erosion. Most of these differences are due to the different settings: the Vrica sediments were deposited in shallower water, with a higher sedimentation rate, and closer to land than the ODP sapropel. Where do we go from here: Chaos or community? Even after several decades of intense research on Mediterranean sapropels, the precise mechanism behind their formation has not been fully elucidated. Clearly, sapropel formation is the result from an intricate interplay of several processes, each with varying intensity in time and place. To improve our understanding of these processes, we primarily need a more detailed knowledge of how palaeoproxies function, and what they register. The ultimate goal should be a model that can explain how sapropels are formed in the eastern and western Mediterranean, from the Miocene to the Holocene. In my view, the only way in which such a model can be attained, is cooperation between all marine disciplines: stratigraphy, sedimentology, micropalaeontology, inorganic and organic geochemistry, palynology, and oceanography. The year 2004 will mark the centennial of the word "sapropel". It would be appropriate if, by then, we will better understand what this term stands for.?Chapter 1 14 Acknowledgements - Stephen Hawking, Charles Darwin, Nicolaus Copernicus and Martin Luther King are acknowledged for their contributions to the section titles of this introduction.?15