Sedimentology (2009) 56, 247266

doi: 10.1111/j.1365-3091.2008.01026.x

TethyanMediterranean organic carbon-rich sediments from Mesozoic black shales to sapropels

KAY-CHRISTIAN EMEIS* and HELM UT WEISSERT *IfBM, University of Hamburg, Hamburg, Germany (E-mail: [email protected]) Geological Institute, ETH Zurich, Zurich, Switzerland
ABSTRACT

The Jurassic to Holocene record of black shale deposition in the TethysMediterranean region is unrivalled by that of any other ocean basin, either in land sections or drill cores. The term black shale is used here broadly for sediments with elevated organic carbon concentrations (> 1%), including the Pliocene to Recent sapropels. Most of the black shales are devoid of benthonic organisms, are laminated, and were deposited in distinct rhythms during periods when the deep waters of the ocean basins were anoxic or dysoxic. The Tethyan black shale records have become essential in studies of the transfer of organic carbon into the sediment record and for astronomical tuning and geological time scales. These records have been central in understanding climate control on ocean dynamics and biogeochemical cycles. The Mesozoic black shales were deposited within well-dened time envelopes of around 05 to 1 Myr. These black shales, which were conned to certain chronostratigraphic intervals in the Jurassic and Cretaceous, were recognized as expressions of global Oceanic Anoxic Events in the mid-1970s and subsequently named after prominent researchers (Bonarelli, Selli, Goguel). The black shale episodes were dated by biostratigraphic methods and by highresolution chemostratigraphy and cyclostratigraphy. Mesozoic black shales are now interpreted as the oceanographic expression of major perturbations of the global carbon cycle and climate. Research into younger (Pliocene to Pleistocene) sedimentary cycles (including black shales, termed sapropels) exposed in land sections, or found in pelagic and hemipelagic marine sediment cores of Late Quaternary age, started in the 1950s. Main threads pursued from this end of the record were the climatic control of oceanic processes that permitted the development of highly detailed and precise time scales tuned to the astronomical clock of insolation changes, palaeoclimate evolution of the circum-Mediterranean area and biogeochemical dynamics in anoxic basins. After 50 years of intensive research, the Tethyan and Mediterranean black shales remain subjects of fascination in Earth Science. Tracing the origins and building upon recent progress, the current hypotheses on their formation are reviewed here. It is a panorama of complex interplays between global and regional tectonics, climate dynamics during both Ice House and Greenhouse states of global and regional climate, oceanographic responses to these climate changes, and biogeochemical adaptations that were all needed to shape an extraordinary archive of global change in the absence of human activity. Keywords Mesozoic black shale, Oceanic Anoxic Event (OAE), organic carbon-rich sediment, sapropel

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K.-C. Emeis and H. Weissert petrography and their palynology. The petroleum potential of bituminous sediments was investigated and their geochemical characteristics and possible origins of organic carbon-enriched sedimentary rocks were established (Bray & Evans, 1965; Vine & Tourtelot, 1970; Welte, 1972). These investigations clearly demonstrated that black shales were unevenly distributed in space and time but subsequent research and exploration determined that the vast majority of petroleum reserves and source rocks were clustered in the Tethyan realm. It also became clear that strata from two geological periods, the Late Jurassic and the Early to Middle Cretaceous, were responsible for > 50% of the known generated petroleum (Klemme & Ulmishek, 1991) (Fig. 1). After industrial production of oil started in Western and Central Europe, it quickly spread offshore. Since then, a vast literature base has accumulated on the sedimentary, palaeontological and geochemical aspects of black shales as a petroleum source and as a geological archive of past states of the Earth. The second arena where work on organic carbon-rich sediments broke ground in the Mediterranean realm was the Neogene sapropel record. The term sapropel dates back to the turn of the 20th Century and was proposed as the international term for the German word Faulschlamm (Potonie, 1904). Since then it has been used in a generic sense to describe ne-grained and unconsolidated sediments rich in organic matter deposited in stagnant water and also to denote distinct dark layers (sapropelites) interbedded in organic carbon-poor host sediments.

INTRODUCTION AND HISTORY OF RESEARCH Black shales have been and remain difcult to dene and they are hard to categorize. A common characteristic is an enrichment of organic carbon of up to 7%, and rarely up to 15% (Bitterli, 1963; Hallam & Bradshaw, 1979), but organic carbon content up to 30% is known from Pliocene sapropels and black shales of Cenomanian age. These shales tend to be different from the surrounding host rocks: visually, chemically and in facies. In terms of sedimentology, distinction is often much less straightforward (Spears, 1980) and occasionally they leave no visual trace when oxidized. Black shales or sapropelites (Potonie, 1904) occur in all aquatic sedimentary settings but the ones which are dealt with here are marine hemipelagic or pelagic muds or mudrocks, bioturbated or laminated, with or without carbonate, sometimes siliceous, with organic carbon > 1% to 2% of marine or terrestrial origin and frequently enriched in trace metals. These shales are interbedded commonly in sediments lacking organic carbon enrichment, and are often members of cycles that have time periods in the range of tens to hundreds of thousands of years (Vine & Tourtelot, 1970; Kidd et al., 1978; Hallam, 1980; Arthur et al., 1984; Jones, 1987; Arthur & Sageman, 1994). Organic carbon-rich sediments, known as bituminous rocks, as sapropels or simply as black mudstones, shales or marls have attracted geologists since the days when Leopold von Buch (1839) introduced the term Schwarzer Jura into stratigraphic nomenclature. The dark shale successions consisting of the Posidonien-Schiefer and Opalinuston were deposited during the Early Jurassic (Lias-Dogger) in a shallow epicontinental sea covering wide parts of Northwestern Europe. Several authors investigated the process of bituminization as early as the very beginning of the 20th Century (see reviews in Bitterli, 1963; Arthur et al., 1984). After World War II, the Posidonien-Schiefer became one of the prominent research targets for the petroleum industry in Europe. In a research project between 1950 and 1960, Koninklijke Shell investigated Tethyan organic carbon-enriched sedimentary rocks throughout Western Europe. Petroleum research focused on nding the appropriate structural settings for source rocks and reservoirs, with ancillary work on the possible origin of organic carbon-enriched sedimentary rocks. Shell researchers analysed almost 1600 samples for their chemical composition, their sedimentary

The Mediterranean sapropels

One motivation for sapropel research was to establish the stratigraphy of the Neogene. Work centred on the beautiful exposures of geologically young and tectonically uplifted marine sediments in Southern Italy, Greece and other places in the Mediterranean Sea basin (Selli et al., 1977). In the land exposures, the sedimentary cycles are barely recognized as containing black shales (Meulenkamp et al., 1979) that were oxidized and preserved only as marl layers. However, it quickly became clear after the Swedish Deep-Sea Expedition in 1947 to 1948 that matching organic carbon-rich sapropel intervals occur in recent Pleistocene sediments (Kullenberg, 1952; Olausson, 1961) and, after drilling by the Deep Sea Drilling Project (DSDP)

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Fig. 1. (A) Petroleum realms, realm areas and percentage of petroleum reserves per area and (B) stratigraphic age of petroleum source rocks (after Klemme & Ulmishek, 1991).

and the Ocean Drilling Program (ODP), throughout the entire post-Miocene period (Ryan & Hsu, 1973; Hsu & Montadert, 1978; Kidd et al., 1978)

and in the entire Mediterranean Sea basin (Kastens et al., 1987; Comas et al., 1996; Emeis et al., 1996).

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K.-C. Emeis and H. Weissert theory of sea oor spreading, the DSDP also provided a wealth of new geological data on the evolution of Mesozoic and Cenozoic oceans. New research in the eld of sedimentology shifted from shallow-water to pelagic and deep-sea sediments (Hsu & Jenkyns, 1974). Information on Mesozoic ocean history, mainly originating from research in the Mediterranean region, was broadened greatly, in that data from continental margins could be combined with an increasing amount of data from pelagic and deep-sea environments. Bernoulli (1972) recognized close similarities between Tethyan Mesozoic deep-sea sediments and sediments recovered by drilling from the North Atlantic Ocean. Bernoulli was able to correlate a prominent, up to 2 m thick black shale stratum found in Tethyan sediments of Middle Cretaceous age with a corresponding black shale level at DSDP Sites 101 and 105. Schlanger & Jenkyns (1976) proposed that discrete and isochronous black shale horizons were not limited to the Atlantic and Tethys Oceans but that they occurred globally. These authors proposed that the widespread occurrence of these black shales was related to global sea-level and proposed Oceanic Anoxic Events (OAE) of global extension. Based on DSDP and Tethys Ocean data, Schlanger and Jenkyns dened two OAEs. The AptianAlbian OAE covered millions of years, whereas the CenomanianTuronian OAE was of shorter duration (< 1 Myr). Additional OAEs were identied later (ConiacianSantonian, Valanginian, Toarcian) and OAEs have been reinterpreted as time envelopes within which organic carbonrich sediments were formed episodically on a global scale (Jenkyns, 1980). Even if the initial hypothesis on the dominating role of sea-level did not stand up to detailed study, interdisciplinary studies revealed a correspondence of OAEs with phases of increased ocean crust formation and the emplacement of Large Igneous Provinces (LIPs; Larson, 1991). Today, a clear link between volcanism and black shale formation is established in the Aptian with the LIP of the Ontong-Java plateau (Larson, 1991) and Weissert et al. (1998) proposed a coincidence between Parana volcanism and the Valanginian OAE.

The presence of anoxic layers in the geological record of the Eastern Mediterranean Sea had been postulated as a reaction to sea-level lowering in the glacial Mediterranean Sea (Bradley, 1938). After these layers had been recovered in cores, Kullenberg (1952) thought that they indicated anoxic conditions, brought about by stagnation during pluvial conditions in glacial periods. However, in the mid-1950s, it was recognized that the youngest sapropel post-dated the glacial and the glacially lowered sea-level, so that the original idea of Bradley and Kullenberg was rejected. Investigations of faunal (Parker, 1958) and isotopic (Emiliani, 1955) properties suggested pronounced coldwarm cycles in the Late Pleistocene, and Olausson (1961) established that most sapropels occurred after major cool periods. Excellent reviews of the status of knowledge (and ignorance) in the 1970s are given in Ryan (1972) and Ryan & Cita (1977). In combination with tephra layers (Keller et al., 1978), the characteristic sequence of sapropel layers (named S1 to S12) in sediment cores of the Late Quaternary proved to be an excellent tool for stratigraphic purposes. The observed temporal pattern of sapropel deposition was clearly paced by climate (Cita et al., 1977; Vergnaud-Grazzini et al., 1977) and, in seminal papers by RossignolStrick (1983, 1985), were found to be locked to the orbital rhythms of precession and eccentricity. The temporal link is so robust that the astronomically tuned stratigraphy (Hilgen, 1991), established from Mediterranean sediment cycles exposed on land and recovered by scientic ocean drilling, set the standard for Pliocene and Quaternary chronostratigraphy worldwide (Lourens et al., 2004). Sapropel and geochemical records even have been used to reconstruct changes in tidal dissipation and dynamical ellipticity of the orbit of the Earth because of mass load variations induced by glacialinterglacial cycles (Lourens et al., 2001).

OCEANIC ANOXIC EVENTS GLOBAL AND REGIONAL The concept of plate tectonics had a profound impact on research targets and research questions in Earth history. For the rst time a global framework existed not only for tectonics but also for the newly developing eld of palaeoceanography (Hsu, 1976). With the inception of the DSDP, a new phase in black shale research was initiated. While its rst target was testing the

Tethyan archives for the Mesozoic OAEs

Complementary to the DSDP/ODP record, Mesozoic pelagic and hemipelagic sediments formed in the Alpine Tethys Ocean became a prime target in black shale research (see Fig. 2A, B and C for

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A B D

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172.3633

Fig. 2. Examples of black shales and sapropels in drill cores: (A) Close-up of the lower Albian black shale in ODP Hole 1049C (Blake Nose) that is time equivalent to Oceanic Anoxic Event 1b (photograph courtesy of J. Erbacher). (B) AptianAlbian shales intercalated with quartz sandstones in a hemipelagic Tethyan setting (Zone Sion-Courmayeur, Val Ferret, W. Switzerland). Hammer for scale is 25 cm long. (C) Black shale levels alternating with pelagic limestones (Barremian and Aptian, S. Alps, S. Switzerland and N. Italy), the limestone bed on the right is 10 cm thick. (D) Core photograph showing black sapropels intercalated in calcareous oozes of Pliocene age (504 to 595 m below sea oor) at ODP Site 969 (Eastern Mediterranean Sea). In sections 5 and 6, and in the core catcher, sapropel ghosts are regularly spaced reddish brown layers. Each section is 150 cm long.

examples). The CenomanianTuronian, Aptian, Valanginian and Toarcian black shales were rst identied in numerous pelagic sections from the Appennines and Southern Alps (Italy) and in hemipelagic successions from the Vocontian Trough (Jenkyns, 1980; Arthur & Premoli-Silva, 1982; Breheret, 1985; Weissert et al., 1985). Most of these black shales were deposited in deep-water environments of more than 1 km water depth. The OAE time envelopes marking episodes of increased black shale formation in the Cretaceous were redened and dated with biostratigraphic, magnetostratigraphic and chemostratigraphic methods (Alvarez et al., 1977; Channell et al., 1993) and were renamed after early workers in the eld of black shales. The organic-rich sediments of the Livello Bonarelli were deposited at the very end of the Cenomanian within a few tens to a

few hundred kiloyears (Tsikos et al., 2004). The black shalelimestone/marlstone succession of the Livello Selli (Wezel, 1985; Coccioni et al., 1987) or Niveau Goguel (Breheret, 1988) accumulated within 1 Myr in the Early Aptian and corresponds to OAE 1a. The durations of Livello Selli and Livello Bonarelli were calculated with cyclostratigraphic methods (Herbert, 1992; Wissler et al., 2003; Kuhnt et al., 2005). Other black shale intervals were recognized in the Albian (e.g. OAE 1b or Niveau Paquier (Breheret, 1985), in the Hauterivian (Faraoni Level; Baudin et al., 1999), in the Valanginian (Barrande layers; Reboulet et al., 2003; or Weissert Event; Erba et al., 2004) and in the Toarcian (Jenkyns & Clayton, 1986). These intervals were identied as either of regional (Faraoni Level) or of global extent (Valanginian, Toarcian black shales).

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K.-C. Emeis and H. Weissert TECTONIC AND CLIMATIC SETTINGS OF BLACK SHALE DEPOSITION Early on, the kingpins of the environmental signicance of black shales were put into place: Bitterli (1963) proposed that bituminous sediments mark turning points in palaeogeographic history (e.g. orogeny, eustasy) followed by prolic plankton production and by stagnation during warm and moist climate. The Cretaceous was a greenhouse time (Chamberlin & Salisbury, 1906), when enhanced volcanic activity increased the volumes of mid-ocean ridges (Pitman, 1978) and raised both global atmospheric carbon dioxide levels (Berner, 1991) and global sea-level (Haq et al., 1987). These effects resulted in high temperatures, high weathering rates and a peculiar ocean circulation pattern described as sluggish by the early investigators. The high latitudes were ice-free, the latitudinal temperature contrast was weak (Barron & Peterson, 1990) and, with ocean basins elongated in east-west rather than in the present north-south orientation, ocean circulation was very different from that prevailing today (Brass et al., 1982; Barron & Peterson, 1990; Haupt & Seidov, 2001). An important difference was that deep water formed at low latitudes in the Eastern Tethys and that the rate of deep-water formation was susceptible to variations in global temperature and in monsoonal moisture transport. It had been realized that black shales were formed as the result of oceanographic changes controlled by Cretaceous plate tectonics (see summary in Weissert, 1981) and rising sea-level (Jenkyns, 1980). The inuence of sea-level was obvious in creating fertile, shallow marginal seas with the potential to export organic matter into young offshore basins, as well as for advection of oxygen-depleted water masses from these marginal seas far out into the open ocean (Hallam & Bradshaw, 1979; Jenkyns, 1980). Schlanger & Jenkyns (1976) and Thiede & Van Andel (1977) proposed that mid-water oxygen minimum zones were responsible for black shale formation in the Pacic. Advection of shelf organic matter was seen as a signicant factor for black shale formation in the Atlantic and Caribbean Basins, where the contribution of terrestrial organic matter was signicant (Jansa et al., 1979; Degens et al., 1986). When attempting to decipher the causes, processes and sequence of events leading to black shale deposits, it is found that Mesozoic black shales have disadvantages in stratigraphy, preservation or comparison with recent analogues. Studies on these topics have concentrated on

Mediterranean archives for Late Neogene sapropels

The most complete and undisturbed record of marine sapropel sequences in the Mediterranean Sea was recovered during ODP Legs 160 and 161 that specically set out to clarify the palaeoenvironmental history of this sea and the sequence of Pliocene to Holocene sapropel events. Many conventional gravity cores from the Eastern Mediterranean Sea and material from DSDP Legs 13 and 42A were the basis for planning these drilling campaigns (Ryan, 1972; Ryan & Hsu, 1973; McCoy, 1974; Kidd et al., 1978). The ODP drilling of a transect of sites recovered several complete Pliocene to Holocene sediment sequences that represent a range of depositional environments, water depths and oceanographic and biological provinces in the modern Mediterranean (Comas et al., 1996; Emeis et al., 1996). In the drill cores from the Eastern Mediterranean Sea, a record containing more than 80 individual sapropel events was recovered from Pliocene to Holocene age. The sapropels at the drill sites of Leg 160 were correlated with the astronomical rhythms of precession, tilt and eccentricity (Emeis et al., 2000), and with land exposures of the same age (Lourens, 2004). In the Western Mediterranean Sea, the sapropel record was found to extend only to approximately 2 Ma and was less complete (Cramp & OSullivan, 1999; de Kaenel et al., 1999). The Eastern Mediterranean sapropels occur in distinctive packets that often are separated by intervals of yellowish-brown, oxidized sediment (Fig. 2D). Many individual sapropels are extraordinarily rich in organic carbon (up to 30% by weight and predominantly marine in origin), many are at least in part laminated and range in thickness between a few centimetres and metres. Other sapropels are bioturbated or oxidized to a considerable extent and discernable only as burnt-out ghosts of reddish carbonate oozes with tell-tale chemical or magnetic properties. During certain periods, diagenetic overprinting has apparently occurred in the entire Eastern Mediterranean basin, leading to isochronous, reddish sediment packages that may encompass several hundreds of thousands of years (e.g. between 1 and 07 Myr). Composite sapropel and isotope records showed that the climate inuence changed from obliquity and precession forcing in the period from 32 to 19 Myr to dominant obliquity inuence in the period from 19 to 1 Myr; in the last million years, all orbital cycles were clearly expressed (Kroon et al., 1998).

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TethyanMediterranean sediments from Mesozoic black shales to sapropels much younger and analogous sapropels, but Erbacher et al. (2001) explicitly pointed out parallels between emerging models for Mesozoic Black Shale and those used to explain Pliocene Holocene sapropel formation in the Mediterranean Sea. Clearly, the hypotheses on underlying principles of black shale and sapropel deposition in the respective scientic communities appear to converge (Herrle et al., 2003). In both cases, the climatic forcing at Milankovitch frequencies is invoked and translates into: (i) changes in the monsoon system; (ii) increased moisture advection; and (iii) changes in the water mass circulation of the Mediterranean Sea (and Tethys). Sapropel periods were preceded by and coincided with an increase in the density contrast between surface and deep waters and in decreasing oxygen supply to the deep basins. Surface water density decreased because of the combined effects of warming and freshening, so that the cold and salty deep water the old deep water formed during preceding cold climatic stages prevented deep convection of oxygenated surface water. Both freshening and increasing sea surface temperature (SST) of surface water are indicated by a variety of oral, faunal, isotopic and geochemical proxies. Deep waters in the basins became anoxic after their dissolved oxygen was depleted several hundreds to thousands of years after convection ceased. The climatic trigger for hydrographic changes and sapropel formation is still not identied with certainty and there is reason to believe that several acted in concert. The original hypothesis (Olausson, 1961) was that in the Late Quaternary ice sheet melt water from the northern catchment (via the Black Sea) triggered stratication and stagnation. Timing discrepancies with Black Sea ushing, the very regular temporal pattern of sapropels during the Pliocene and the absence of ice on the Northern Hemisphere are arguments against this hypothesis. The northern catchment of the Eastern Mediterranean Sea may have received increased precipitation during maximum insolation, leading to decreased salinity in the deep-water formation areas (Rohling & Hilgen, 1991). However, since approximately 600 ka, some sapropels formed during glacials or cold stadials that make runoff from the northern catchment unlikely and create conditions adverse to water-column stratication, in general. Rohling (1994) suggested a link between deep-water stagnation in the Mediterranean basins with deglacial sea-level rise and surface water freshening in the Atlantic Ocean and

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enhanced inow of Atlantic surface water over considerably denser cold and saline Mediterra nean water. Bethoux & Pierre (1999) suggested the same link as a primary inuence responsible for the formation of sapropels in the Western Mediterranean Sea. The effects of rising sea-level and embedded melt water pulses, as well as the effect of Black Sea fresh water outow following connection to the Aegean Sea, were modelled by Matthiesen & Haines (2003). These calculations suggest that the effects of meltwater pulses increased stratication in the Mediterranean Sea by 21% (meltwater pulse 1A around 12 ka) and 14% (meltwater pulsepulse 1B around 95 ka). Gradual opening of the Black Sea increased stratication by 13% and catastrophic opening by 43%. Several sapropels formed when the Eastern Mediterranean Sea was in a glacial mode, as suggested by cold SST estimates and pollen assemblages (e.g. S6 at around 176 ka, S8 at around 220 ka). Sapropel formation under glacial conditions in the Late Quaternary is a strong argument for a source of fresh water in the monsoon system of Africa. A systematic correlation exists between the distribution of sapropels and maxima of monsoon index which is a function of precession and eccentricity controlled insolation (Rossignol-Strick, 1983, 1985). Maxima in the monsoon index coincide with the formation of cold sapropels S6 and S8 and point to an intensied African monsoon during northern summer. This effect enhanced precipitation in tropical Ethiopia and, thus, enhanced ood discharge of the Blue Nile River. In this hypothesis, sapropel formation would be linked closely to northern tropical and even southern hemisphere climate. Recent modelling experiments suggest that Nile discharge alone was not sufcient to explain the long-lasting enhanced stratication (Tuenter, 2004). Additionally, enhanced northward migration of the Intertropical Convergence Zone (the meteorological equator) into the southern catchment of the Mediterranean Sea has been proposed for sapropel periods at obliquity maxima; this would have channelled tropical rainfall into the Mediterranean Sea through what is now the Sahara Desert (Rohling et al., 2002). A further possible source of fresh water is the Mediterranean Sea itself, which today provides 40% of precipitation in its own catchment. Almost all sapropels (except the cold S6 and S8) coincide with signicant warming of surface waters at the transition from cold to warm climatic periods. This warming would, on the

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K.-C. Emeis and H. Weissert The Neogene sapropel and Mesozoic black shale material recovered by drilling marine sequences has been found to be considerably less altered by diagenesis and weathering than land exposures and evidence from geochemical and mineralogical analyses has helped to constrain the depositional environment. With this information at hand, the arguments can be evaluated on whether enhanced preservation (under anoxic conditions) or enhanced biological productivity was the root cause for organic carbon enrichment in black shales and sapropels (Calvert, 1987; Pedersen & Calvert, 1990). Much of the data gathered on sapropels and black shales support the hypothesis of low-oxygen or anoxic conditions during black shale formation, paired with (or accelerated and in part caused by) an increase in biological productivity (Calvert et al., 1992; Struck et al., 2001; Kuypers et al., 2002; Herrle et al., 2003). The Mediterranean Sea was anoxic during sapropel deposition but not as extremely and lastingly as the modern Black Sea the type euxinic basin is today. Because the shallowest visible sapropels were found below a modern water depth of 400 m, it was originally thought that waters below that depth in the Eastern Mediterranean were anoxic. Anastasakis & Stanley (1986) suggested that time lags existed between the onset of sapropel conditions between different basins and water depths during sapropel deposition, a concept that was later reformulated by Strohle & Krom (1997) to indicate changes in the extent and severity of oxygen depletion in a mid-water oxygen minimum zone. Spatially resolved studies on benthonic fauna during isochronous sapropel events changed the view of completely anoxic deep-water masses; depth transects across northern sub-basins (Adriatic and Aegean Sea both are areas of deep-water formation today) suggest that the deep-water oxygen content continued to support impoverished benthonic fauna throughout periods of sapropel deposition (Casford et al., 2003); the same holds for the main basins. In the S5 sapropel [transition from Marine Isotope Stage (MIS) 6 to MIS 5; around 127 ka], benthonic foraminifera indeed vanish for some time (several hundreds to thousands of years) shortly after the onset of organic-rich sedimentation. However, a low oxygen fauna often returns within the visible sapropel layer and several sapropels show either continuous benthonic populations (Jorissen, 1999; Schmiedl et al., 2003) or intermittent, in part regional, reoxygenation events (Rohling

one hand, enhance the stratication of water masses and would, on the other hand, result in increased evaporation in the entire Mediterranean Sea and rainfall specically in the Eastern Mediterranean catchment (and further east), effectively pooling fresh and warm waters at the sea surface and impeding deep-water formation (Rohling & Hilgen, 1991; Rohling, 1994; Emeis et al., 2003; Tuenter, 2004). This concept is supported by observations on isotopic composition of connate waters in speleothems of Israel which suggest greatly enhanced precipitation rates on land adjacent to the Levantine Basin during sapropel events. This rain had an isotopic composition that followed the Mediterranean Meteoric Water line (Bar-Matthews et al., 2003) except during periods corresponding to cold sapropel S6 and S8 deposition. The climatic cause of these sapropel events is still not explained, although modelling experiments implicate glacially lowered evaporation rates and enhanced runoff from the Nile and thus the African (and Indian) low-latitude monsoon systems (Masson et al., 2000). It is most probable that several sources of moisture, each with a specic timing in relation to insolation, warming and related low-latitude and high-latitude climate processes, succeeded each other and together created the very special conditions in the Mediterranean Sea. Recent recognition that Mesozoic OAEs are also rhythmic and composed of individual layers (Menegatti et al., 1998; Herrle et al., 2003) may point to a similar external forcing.

PRODUCTIVITY OR PRESERVATION? The publication by Schlanger & Jenkyns (1976) was the starting point of a new episode of black shale research. In numerous publications, researchers discussed causes and consequences of black shale formation. Did black shales form under anoxic or dysoxic conditions related to basin-wide stratication of water masses? Were they the results of turbidity currents transporting large amounts of terrestrial organic matter from land into the deep sea? Was productivity during the time of black shale formation exceptionally high? Very early on, the debates concentrated on hydrological changes associated with black shale and sapropel deposition and the roles of productivity and anoxia in accumulating organic matter in sediments (see Weissert, 1981 for an early summary).

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TethyanMediterranean sediments from Mesozoic black shales to sapropels et al., 1997; Casford et al., 2003; Schmiedl et al., 2003). This observation implies that convection and deep-water formation in the northern basins continued and that oxygen recharge by convection was not shut off completely. Benthonic fauna in depth transects of isochronous sapropels suggest that convection reached down to around 1000 to 2000 m fairly regularly and occasionally supplied oxygen even to the deepest sea oors. Although in low numbers, benthonic foraminifera also persisted in OAE 1b of the Mesozoic (Herrle et al., 2003). Bioturbation structures in many of the black shales deposited during the OAE 1a are further evidence for a benthonic fauna surviving in poorly oxygenated deep-water environments. Molecular fossils characteristic of bacterial pigments specic to green sulphur bacteria support the hypothesis of anoxic conditions in the water column during deposition of Pliocene/ Pleistocene sapropels and black shales (Menzel et al., 2002; Pancost et al., 2004; Wagner et al., 2004). However, in the light of the distribution patterns of benthonic foraminifera, the occurrence of these markers also poses a problem. Nowadays, the strictly anaerobic bacteria that produce the pigments are known from stagnant ponds and lakes and recently have been identied as major primary producers in a deep chlorophyll maximum zone in the anoxic Black Sea. These bacteria require the combination of light and hydrogen sulphide-containing waters. The presence of their biomarkers in black shales and sapropels thus supports the concept that a chemocline separates oxic and anoxic waters; however, it must have existed above the 01% light level that appears to be the lower end of their photosynthesis range. Until palaeo-depth patterns of the chemocline and associated bacterial photosynthesis and benthonic faunas alike have been claried, the exact vertical segregation into anoxic, suboxic and oxic water zones in midwater remains open. However, with evidence for sulphidic waters from sulphur speciation studies (Passier et al., 1999) and lamination found in many sapropels, there are four independent arguments for anoxia during at least some stages of sapropel and black shale deposition. Anoxia has an effect on the preservation of organic matter in marine sediments (Demaison & Moore, 1980; Emerson & Hedges, 1988) and causes signicantly higher concentrations of palynomorphs and individual lipids in sapropels than in surrounding oxic sediments (Cheddadi & Rossignol-Strick, 1995; Bouloubassi et al., 1999). Biological productivity at the sea

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surface is among the primary factors controlling concentration and accumulation of organic carbon in sea oor sediments (Suess, 1980), together with sedimentation rate (sealing factor) and oxygen content at the sedimentwater interface (Muller & Suess, 1979; Caneld, 1994). Because the sedimentation rate found in most sapropel layers of Late Pleistocene age is equal to or higher than that in surrounding calcareous oozes, the enrichment in organic carbon in sapropels cannot be explained by decreased dilution with other sedimentary components at equal ux rates of organic carbon. The signicant enrichment in sapropels thus requires substantially higher biological production than that found in the Mediterranean Sea today, even under anoxic conditions that favour the preservation of organic matter (Howell & Thunell, 1992). Independent evidence for higher productivity comes from distribution patterns of benthonic foraminifera and chemical analyses of productivity proxies. Assemblages of benthonic foraminifera have higher numbers of individuals and a change to faunas indicative of higher benthonic uxes of organic matter (Schmiedl et al., 2003) before and after anoxic periods; the accumulation rates of barium and Ba/Al ratios (Mercone et al., 2000; Weldeab et al., 2003) and opal accumulation rates were high (Kemp et al., 1999). Organic geochemical and palynological data suggest that the bulk of organic carbon in sapropels and older black shales is dominantly from marine sources, with land-plant material consistently present in only subordinate amounts (Bouloubassi et al., 1999; Hochuli et al., 1999). Views differ on the mechanisms that enhanced productivity. In some well-preserved Mediterranean sapropels, detailed investigation of diatom assemblages has been possible because of unusually good preservation of the opaline silica that in many marine sediments is usually lost to dissolution (Schrader & Matherne, 1981; Kemp et al., 1999). The best preserved sequences were rich in fragile diatom mats that form a pronounced set of laminations, including possible annual bloom layers. The ora is indicative of sloping isopycnals and stratication found in association with hydrographic frontal systems. The diatoms are adapted to migrate between a nutrient-rich lower water body of the front and nutrient-poor upper water. Collecting near the interface between the upper and lower water mass in the front, the disintegration of slowly grown mats sporadically resulted in large ux rates of opal and organic matter to the sea oor.

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K.-C. Emeis and H. Weissert ratio of reactive nitrogen over phosphate, so that phytoplankton is limited by nitrate. Cyanobacteria use the remaining phosphate (and organically bound phosphate that is not accessible to other plankton) and convert it to organic matter (see review article by Karl et al., 2002 for details). Decaying cyanobacterial biomass supplies phosphate and nitrate that can be assimilated by other phytoplankton (Tyrrell, 1999). Thus, to increase productivity and organic matter ux during sapropel times, new phosphorus (Eppley & Peterson, 1979) had to enter the water column in the Mediterranean Sea to stimulate cyanobacterial blooms. The only plausible source is sediments overlain by anoxic waters (van Cappellen & Ingall, 1994; Wallmann, 2003). Under the anoxic conditions in near-bottom waters, phosphorus leaked out from sediments into the deep-water body, as indicated by the very high ratios of organic carbon to phosphorus in sapropels (Slomp et al., 2002; see Fig. 3 below). In many black shales and virtually all sapropels that ratio is signicantly higher than the expected molar ratio of 100 of aquatic biomass.

The oral assemblage in the diatomaceous sapropel strengthens the hypothesis of fresh water input as a cause for black shale formation which would result in the development of frontal systems in the sea surface. The microfacies studies provide evidence for anoxic conditions during sapropel formation and suggest that diatoms, even if they are preserved rarely, were a prominent source for the organic matter in sapropels. A possible explanation for the link between anoxia and enhanced productivity comes from studies of nitrogen isotopes. Both in sapropels and most, but not all, black shales, the nitrogen isotope ratio (15N/14N, expressed as d15N) of sedimentary nitrogen is very low (between 0 and 2&). Originally thought to support the hypothesis of enhanced nutrient input from land and decreasing nutrient utilization (Calvert et al., 1992), recent interpretations suggest signicant atmospheric dinitrogen xation by diazotrophic cyanobacteria during sapropel and black shale periods (Struck et al., 2001; Kuypers et al., 2004; see Jenkyns et al., 2001 for exceptions). In biogeochemical terms, that increase in nitrogen xation suggests a decrease in the stoichiometric

Fig. 3. Illustration of the feedback mechanism leading to organic carbon sequestration in the case of Mediterranean sapropels S7 to S5 (marine isotope stages 7 to 5, 103 to 201 ka). Corrected for sea surface temperature changes and global ice effect, the decreased d18 O of planktonic foraminiferal calcite suggests freshening of surface waters by as much as 12 psu at the very base of sapropel layers. Together with increases in SST (determined by alkenone unsaturation ratios) of up to 10 C, this freshening reduced the density of surface waters and convection ceased. Enhanced organic carbon burial was most probably aided not only by enhanced preservation under oxygen-decient conditions at the sea oor but also by the addition of phosphorus from anoxic sediments (indicated by high C:P molar ratios), non-Redeld N:P ratios initially in the deep-water body and after shallow convection also in the euphotic zone and concomitant nitrogen xation (indicated by depleted d15 N ratios of bulk nitrogen). Compiled from Emeis et al. (2003), Struck et al. (2001) and Weldeab et al. (2003). [mbsf = metres below sea oor]
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TethyanMediterranean sediments from Mesozoic black shales to sapropels It is yet unclear how phosphate-rich deep water reached the euphotic zone. Conceivably, ongoing shallow convection periodically or seasonally eroded the pycnocline and chemocline and mixed phosphate-rich and nitrate-poor subpycnocline waters into the biologically active surface water layer. This effect may have caused excess phosphate over nitrate ratios in the euphotic zone, triggering cyanobacterial dinitrogen xation at the oceanatmosphere interface and a concomitant general rise in fertility (see below). Other hypotheses argue that the productivity regime during black shale and sapropel formation remained oligotrophic, because cyanobacterial nitrogen xation today is an indication for low productivity regimes (Rau et al., 1987; Sachs & Repeta, 1999). Clearly, the last words on the productivity/preservation issue have not been spoken.

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BLACK SHALES, CARBON CYCLE AND CLIMATE: A NEGATIVE FEEDBACK IN SYSTEM EARTH? A remarkable shift in black shale research was triggered around 1980 by major new developments in climate research. Investigations on air bubbles frozen in ice cores of Antarctica provided exciting evidence for uctuating carbon dioxide concentration in the atmosphere during glacialinterglacial cycles (Neftel et al., 1982) with high carbon dioxide levels coinciding with warm times during the Late Pleistocene. Carbon dioxide was appreciated newly as a climate forcing gas that acted as an amplier in an orbitally driven Late Neogene climate system. Early in the course of research into Mesozoic OAEs and black shales it became clear that these sequences recorded global perturbations of the carbon cycle and climate. Ryan & Cita (1977) pointed out that the deposition of vast black shale deposits must have had consequences for the global carbon cycle and estimated that 80 1012 g carbon per year were extracted to sediments during these episodes. Weissert et al. (1979) suggested that elevated carbon dioxide levels in the atmosphere could have triggered black shale deposition. Arthur et al. (1984, 1985) developed the rst palaeoclimate models of OAE times. These authors proposed that changes in oceanography were triggered by episodic increase in volcanic carbon dioxide emission that raised pCO2 levels of the atmosphere. In a self-regulated Earth System, climate regulation and regulation

of the carbon cycle were envisioned as a combination of biotic and abiotic processes. Elevated carbon dioxide concentrations were balanced by increased weathering rates (Berner et al., 1983) and by an intensication of the biological carbon pump (Arthur et al., 1988). The global footprints of past carbon cycling emerged from studies with a new tool: stable isotope analyses of sedimentary organic and carbonate carbon. Years after the Craig (1953) fundamental investigation of carbon isotope geochemistry in natural environments, carbon isotope geochemistry was introduced as a new technique in palaeoceanography (Berger et al., 1978). The carbon isotope composition of biogenic carbonate could be used as a proxy for the past sea water carbonate system and short-term uctuations (< 100 kyr) could be related to uctuations within the carbon reservoirs and to changes in surface-water/deep-water gradients caused by changes in ocean circulation. Studies on the Early Mesozoic focused on either longterm trends in carbon isotope records across OAEs, which reected transfers of massive amounts of carbon between carbon reservoirs and depicted effects of altered ows between reservoirs on the isotopic balance of the global carbon cycle (Scholle & Arthur, 1980), or on shorter term and regional uctuations during black shalelimestone cycles which were related to changes in oceanography (Weissert et al., 1979). Many of the early reconstructions of the Mesozoic carbon isotope stratigraphy were done in Tethyan pelagic successions and the carbon isotope records showed considerable uctuations in both inorganic and organic carbon uxes. There were time intervals of up to a million years when biogenic carbonate was enriched in 13C. These positive carbon isotope anomalies in carbonate were interpreted to reect burial of isotopically depleted organic carbon in sediments and, indeed, the positive carbon isotope excursions in the biogenic carbonate minerals of limestones and marls were found to coincide with black shales of OAEs (Fig. 4). Because all carbon reservoirs are linked, burial of isotopically depleted organic carbon had to be reected by all other reservoirs in the sea (dissolved inorganic carbon), the atmosphere and on land (land vegetation, soils). When terrestrial carbon isotope curves had been established for specic time intervals (Grocke et al., 1999), they conrmed that carbon isotope anomalies recorded in both marine and terrestrial organic matter were synchronous and of global

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Fig. 4. Compilation of Late JurassicEarly Cretaceous carbon isotope stratigraphy, major volcanic events, black shale episodes and marine biocalcication crises. Black shales: JA, Niveau Jacob; LS, Selli Level; BA, Barremian black shales; FA, Faraoni Level; WE, Weissert Event or Barrande Layers (modied from Weissert & Erba, 2004).

extent, with positive carbon isotope anomalies as the response signature of the biosphere to altered carbon dioxide levels in the atmosphere due to massive organic carbon sequestration in OAEs. Over the last decades, a complete carbon isotope stratigraphy of organic and inorganic carbon has been established (Weissert et al., 1998; Veizer et al., 1999; Voigt, 2000; Jenkyns et al., 2002; Weissert & Erba, 2004) (see Fig. 4).

A clear relationship between volcanism, carbon isotope excursions and black shale formation has been established in the Aptian and to some extent in the Valanginian (Larson & Erba, 1999; Weissert & Erba, 2004). The main pulse of volcanic activity in the large igneous province of the Ontong-Java Plateau between 123 and 120 Ma coincided with the beginning of the major positive carbon isotope anomaly corresponding to OAE 1a. Volcanic

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TethyanMediterranean sediments from Mesozoic black shales to sapropels carbon dioxide that was added to the Aptian atmosphere triggered the carbon cycle perturbation recorded in the carbon isotope record. Yet, surprising results were obtained by high-resolution carbon isotope studies across the OAE 1a in the Aptian, where Menegatti et al. (1998) could show that the time of black shale formation did not coincide with the most positive carbon isotope values. The OAE 1a coincided only with the beginning of the main positive carbon isotope excursion. In the Valanginian, four minor black shale levels identied in the successions of the Southern Alps and of the Vocontian Trough also coincide with the very beginning of the carbon isotope excursion (Lini et al., 1992; Reboulet et al., 2003).

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Carbon isotopes and methane bursts: an example from the Early Cretaceous
Increasingly detailed studies revealed other puzzling evidence: in several records, the expected positive d13C excursions of carbonates were punctuated by negative isotope anomalies of short duration (Fig. 5). Originally, these anomalies were attributed to diagenesis and lithication, but when carbon isotope investigations of planktonic and benthonic foraminifera across the Palaeocene to Eocene thermal maximum had conrmed the negative carbon isotope pulses, Dickens et al. (1995) proposed, based on earlier

work by Kvenvolden (1988), that the release of isotopically depleted methane (d13C = )50&) stored in clathrates could bring enormous amounts of 12C into the oceanic carbon reservoir. Presently, these negative spikes are generally accepted as expressions of additions of 12C from the geosphere into the atmosphere/ocean system, as a consequence either of rapid methane release at times of warming climate (Grocke et al., 1999; Hesselbo et al., 2000), or by volcanic intrusions into continental margin deposits and associated heat ow anomalies (Jenkyns, 2003; Svensen et al., 2004). Methane release probably was triggered by sudden global warming caused by the greenhouse effect of accelerated volcanic carbon dioxide degassing (Fig. 6). Methane release/oxidation from clathrate dissociation would have further enhanced atmospheric carbon dioxide levels and, thus, global temperature. Warming intensies the hydrological cycle and, in concert with higher pCO2 levels, chemical weathering, which is a powerful sink for carbon dioxide. Higher atmospheric pCO2 levels decreased the pH and carbonate supersaturation of the ocean to the point that nannofossils could not or did not need to calcify (nannoconid crises; Erba & Tremolada, 2004). The ratio of inorganic carbon to organic carbon of sinking biogenic material and sediments decreased. Along the coasts, biocalcication crises related to decreased carbonate

Fig. 5. Representation of negative d13C excursion in pelagic carbonates associated with OAE 1a (Aptian) in NW Sicily. The negative spike at 120 Ma is in temporal agreement with the end of volcanism on the Ontong-Java Plateau in the Western Pacic Ocean and is interpreted as the isotopic expression of gas hydrate release (Jenkyns, 2003).
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K.-C. Emeis and H. Weissert (Fig. 3). Warming surface waters (by as much as 12 C as estimated from the Alkenone Unsaturation Index; SST in the graph) lead to an intensied hydrological cycle and precipitation, and to freshening of surface waters because of changed evaporationprecipitation/runoff balances (indicated by d18O-decreases of surfacedwelling Globigerinoides ruber calcite). Both warming and freshening of surface waters enhanced stratication, inhibited or weakened deep-water formation and oxygen advection to deep-water masses and led to anoxia in deeper water bodies isolated from the atmosphere. Under the anoxic conditions in near-bottom waters, phosphorus leaked out into the deepwater body, as illustrated by the soaring ratios (up to 600) of organic carbon to phosphorus just below and in the sapropel layers (Fig. 3). This observation suggests phosphate-enriched deeper water masses, as they occur today in the Black Sea (Fonselius, 1974). Differing from the Black Sea, convection may have diminished but continued to transfer surface waters (and oxygen) into the intermediate water masses and even deep basins. Benthonic faunas suggest that seasonal or more episodic convection must have continued and it must have seasonally eroded the density boundary separating upper and lower water masses, entraining waters with excess phosphate over reactive nitrogen into the euphotic zone. This condition triggered cyanobacterial dinitrogen xation from the atmosphere (as indicated by low d15N values in the sapropel layers) and added reactive nitrogen from mineralization of cyanobacteria to the water body to adjust nutrient ratios back to Redeld ratios. That added reactive nitrogen enhanced the overall nutrient levels and trophic status in itself a positive feedback mechanism that raises the fertility and productivity in surface waters (Tyrrell, 1999). The sequence of events outlined by changes in temperature, salinity, phosphate content of sediments and nitrogen isotope ratios in a sapropel sequence of Late Quaternary age may reect in great detail a basic negative feedback mechanism of carbon sequestration in black shales that has prevented runaway greenhouse conditions on the Earth throughout its history since the Palaeozoic. Pliocene to Holocene sapropels of the Mediterranean Sea are, thus, excellent showcases for the external forcing mechanisms, internal biogeochemical cycles, trophic relationships, diversity and post-depositional alterations of black shales in a broad sense.

Fig. 6. Components of a negative feedback mechanism that causes increased organic carbon sequestration in sediments; this mechanism may have operated in black shale and sapropel formation alike. Note that both carbon dioxide-induced warming (elevated pCO2 of the atmosphere because of methane pulses and its oxidation) and insolation (in the case of the Mediterranean Sea) may trigger the feedback.

saturation resulted in widespread drowning of carbonate platforms (Wissler et al., 2003). Higher fertility and intensication of organic carbon sequestration in sediments resulted from enhanced nutrient delivery from weathering, from the addition of new phosphate from anoxic sea oors and through bacterial nitrogen xation. Enhanced organic carbon preservation under anoxic conditions and diminishing dilution of organic matter by carbonate, together with weathering, constitute a powerful negative feedback that apparently repeatedly has saved the Earth from runaway greenhouse conditions in the course of the Mesozoic (Weissert, 2000).

Sapropels: an illustration of the biogeochemical feedback

The sapropels are of limited temporal (several thousands of years) and spatial extent (restricted to the modern Mediterranean Sea) and the masses of carbon involved are too small to register on the scale of the global carbon cycle, but the detail hidden in sediment cores is impressive and it may serve to trace very basic causal chains that outline the negative feedback leading to black shales. Even if the physical environment prior to sapropels was not unbalanced by additions of carbon from clathrates, and instead was dictated by insolation cycles or glacialinterglacial transitions, the system does not differentiate between causes: warming was rapid and initiated the kick-start of a negative feedback (organic carbon sequestration in sediments) that keeps carbon dioxide in check

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TethyanMediterranean sediments from Mesozoic black shales to sapropels SUMMARY AND CONCLUSIONS Mesozoic black shales indicate massive perturbations in the global (and specically marine) environment and in the global carbon cycle, driven by large-scale tectonic and climatic changes. Typical process time scales that can be resolved by scientic study are in the order of a million to hundreds of thousands of years. Pliocene to sub-recent black shales (sapropels) do not register on a global scale but they do reect global (mainly climatic) processes. Typical process time scales are from a million years to hundreds of years; thus, they permit the detailed analysis of processes involved in black shale formation. All black shales global or regional are produced by chains of events that translate climate change to oceanographic change, which cause reactions in chemistry and subsequent adaptations of biology and result in enhanced carbon sequestration in the lithosphere. The authors tend to view these shales as a product of a basic negative feedback mechanism that acts against enhanced carbon dioxide concentrations (and concomitant global temperature rise) in the atmosphere. Future Mesozoic black shale research will focus on the improved documentation of the global extent of these events. The impact of a sudden release of carbon dioxide into the atmosphere and oceans on the marine and terrestrial biosphere will be studied in detail across the OAEs and interpretation of causes and consequences of changes in carbon reservoirs and ow rates between reservoirs on the Earth will be aided by increasingly detailed numerical Earth system models. Obvious differences between the various Mesozoic OAEs are recognized but they are far from being understood. A further task at hand for black shale researchers is the identication of a regionally variable response of ocean systems to global shortterm (<100 000 years) orbitally driven changes and to compare them with carbon dioxide-driven changes in climate and oceanography. The tasks at hand for sapropel research are to map conditions on sub-basin scales for isochronous black shale events, to clarify the sequence of climatic events that regularly pushed the Mediterranean Sea into anoxia and to combine highresolution and spatially resolved observations with regional and global climate oceanography and ecosystem model simulations to test the existing and still controversial hypotheses for plausibility (Myers et al., 1998; Stratford et al., 2000; Tuenter, 2004). Only a few studies tried to

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combine Mediterranean sapropel research with Mesozoic black shale research but the Mediterranean sapropel record with its impressive detail is an excellent model for past regional black shale occurrences and should be appreciated for what it is: a black shale mesocosm.

ACKNOWLEDGEMENTS The authors thank the editors of the special volume for their patience and support. The manuscript beneted greatly from reviews by D. Bernoulli, P. Meyers, E. Rohling, P. Swart and an anonymous colleague.

REFERENCES
Alvarez, W., Arthur, M.A., Fischer, A.G., Lowrie, W., Napoleone, G., Premoli Silva, I. and Roggenthien, W.M. (1977) Upper CretaceousPaleocene magnetic stratigraphy at Gubbio, Italy. 5. Type section for Late CretaceousPaleocene Geomagnetic Reversal Time Scale. Geol. Soc. Am. Bull., 88, 383388. Anastasakis, G. and Stanley, D.J. (1986) Uppermost sapropel, eastern Mediterranean: Paleoceanography and stagnation. Natl Geogr. Res. Explor., 2, 179197. Arthur, M.A. and Premoli-Silva, I. (1982) Development of widespread organic carbon-rich strata in the Mediterranen Tethys. In: Nature and Origin of Cretaceous Carbon-rich Facies (Eds S.O. Schlanger and M.B. Cita), pp. 754. Academic Press, London. Arthur, M.A. and Sageman, B.B. (1994) Marine black shales: depositional mechanisms and environments of ancient deposits. Ann. Rev. Earth Pl. Sc., 22, 499551. Arthur, M.A., Dean, W.E. and Stow, D.A.V. (1984) Models for the deposition of Mesozoic-Cenozoic ne-grained organiccarbon-rich sediment in the deep sea. In: Fine-grained Sediments: Deep-water Processes and Facies (Eds D.A.V. Stow and D.J.W. Piper), Spec. Publ. Geol. Soc. London, 15, 527560. Arthur, M.A., Dean, W.E. and Schlanger, S.O. (1985) Variations in the global carbon cycle during the Cretaceous related to climate, volcanism, and changes in atmospheric CO2: Natural variations Archean to present. In: The Carbon Cycle and Atmospheric CO2 (Eds E.T. Sundquist and W.S. Broecker), Am. Geophys. Union Monogr. 32, 504 529. Arthur, M.A., Dean, W.E. and Pratt, L.M. (1988) Geochemical and climatic effects of increased marine organic carbon burial at the Cenomanian/Turonian boundary. Nature, 335, 714717. Bar-Matthews, M., Ayalon, A., Gilmour, M., Matthews, A. and Hawkesworth, C.J. (2003) Sea-land oxygen isotopic relationships from planktonic foraminifera and speleothems in the Eastern Mediterranean region and their implication for paleorainfall during interglacial intervals. Geochim. Cosmochim. Acta, 67, 31813199. Barron, E.J. and Peterson, W.H. (1990) Mid-Cretaceous ocean circulation: results from model sensitivity studies. Paleoceanography, 5, 319337.

2009 The Authors. Journal compilation 2009 International Association of Sedimentologists, Sedimentology, 56, 247266

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K.-C. Emeis and H. Weissert

Casford, J.S.L., Rohling, E.J., Abu-Zied, R.H., Fontanier, C., Jorrissen, F.J., Leng, M.J., Schmiedl, G. and Thomson, J. (2003) A dynamic concept for eastern Mediterranean circulation and oxygenation during sapropel formation. Palaeogeogr. Palaeoclimatol. Palaeoecol., 190, 103119. Chamberlin, T.C. and Salisbury, R.D. (1906) Geology, 3 volumes. John Murray, London. Channell, J.E.T., Erba, E. and Lini, A. (1993) Magnetostratigraphic Calibration Of The Late Valanginian Carbon-Isotope Event In Pelagic Limestones From Northern Italy And Switzerland. Earth Planet. Sci. Lett., 118, 145166. Cheddadi, R. and Rossignol-Strick, M. (1995) Improved preservation of organic matter and pollen in Eastern Mediterranean sapropels. Paleoceanography, 10, 301309. Cita, M.B., Vergnaud-Grazzini, C., Robert, C., Chamley, H., Ciaran, N. and DOnofrio, S. (1977) Paleoclimatic record of a long deep-sea core from the eastern Mediterranean. Quatern. Res., 8, 205235. Coccioni, R., Nesci, O., Tramontana, M., Wezel, C.F. and Moretti, E. (1987) Descrizione di un livello guida radiolaritico bituminoso ittiolitico alla base delle Marne a Fucoidi nell Appennino umbro marchigiano. Boll. Soc. Geol. Ital., 106, 183192. Comas, M.C., Zahn, R. and Klaus, A. (Eds) (1996) Proceedings ODP, Initial Results, Vol. 161. Ocean Drilling Program, College Station, TX, 1023 pp. Craig, H. (1953) The geochemistry of the stable carbon isotopes. Geochim. Cosmochim. Acta, 3, 5392. Cramp, A. and OSullivan, G. (1999) Neogene sapropels in the Mediterranean: a review. Mar. Geol., 153, 1128. Degens, E.T., Emeis, K.-C., Mycke, B. and Wiesner, M.G. (1986) Turbidites, the principal mechanism yielding black shales in the early deep Atlantic Ocean. In: North Atlantic Palaeoceanography (Eds C.P. Summerhayes and N.J. Shackleton), pp. 361376. Blackwells, London. Demaison, G.J. and Moore, G.T. (1980) Anoxic environments and oil source bed genesis. Am. Assoc. Petrol. Geol. Bull., 64/8, 11791209. Dickens, G.R., ONeil, J.R., Rea, D.K. and Owen, R.M. (1995) Dissociation of oceanic methane hydrate as a cause of the carbon-isotope excursion at the end of the Paleocene. Paleoceanography, 10, 965971. Emeis, K.-C., Robertson, A.E.S., Richter, C., Blanc-Valleron, M.M., Bouloubassi, I., Brumsack, H.-J., Cramp, A., De Lange, G.J., Di Stefano, E., Flecker, R., Frankel, E., Howell, M.W., Janecek, T.R., Jurado-Rodriguez, M.-J., Kemp, A.E.S., Koizumi, I., Kopf, A., Major, C.O., Mart, Y., Prib now, D.F.C., Rabaute, A., Roberts, A.P., Rullkotter, J.H., Sakamoto, T., Spezzaferri, S., Staerker, T.S., Stoner, J.S., Whiting, B.M. and Woodside, J.M. (1996) Proc. ODP: Initial Reports. Vol. 160. Ocean Drilling Program, College Station, TX, 972 pp. Emeis, K.-C., Sakamoto, T., Wehausen, R. and Brumsack, H.J. (2000) The sapropel record of the Eastern Mediterranean Sea results of Ocean Drilling Program Leg 160. Palaeogeogr. Palaeoclimatol. Palaeoecol., 158, 371395. Emeis, K.-C., Schulz, H., Struck, U., Rossignol-Strick, M., Erlenkeuser, H., Howell, M.W., Kroon, D., Mackensen, H., Ishizuka, S., Oba, T., Sakamoto, T. and Koizumi, I. (2003) Eastern Mediterranean surface water temperatures and d18O composition during deposition of sapropels in the late Quaternary. Paleoceanography, 18, 51 to 518. Emerson, S. and Hedges, J.I. (1988) Processes controlling the organic carbon content of open ocean sediments. Paleocenography, 3, 621634.

Baudin, F., Bulot, L.G., Cecca, F., Coccioni, R., Gardin, S. and Renard, M. (1999) An equivalent of the Faraoni Level in the South-East of France, possible evidence for a late Hauterivian anoxic event in the Mediterranean Tethys. Bulletin De La Societe Geologique De France, 170, 487498. Berger, W.H., Diester-Haas, L. and Killingley, J.S. (1978) Upwelling off Northwest Africa: the Holocene decrease as seen in carbon isotopes and sedimentological indicators. Oceanol. Acta, 1, 17. Berner, R.A. (1991) A model for atmospheric CO2 over Phanerozoic time. Am. J. Sci., 291, 339376. Berner, R.A., Lasaga, A.C. and Garrels, R.M. (1983) The carbonate-silicate geochemical cycle and its effect on atmospheric carbon-dioxide over the past 100 million years. Am. J. Sci., 283, 641683. Bernoulli, D. (1972) North Atlantic and Mediterranean Mesozoic Facies, a comparison. In: Init. Reports of the Deep Sea Drilling Project, 11 (Eds C.D. Hollister, J.L. Ewing, D. Habib, J.C. Hathaway, Y. Lancelot, H. Luterbacher, F.J. Paulus, C.W. Poag, J.A. Wilcoxon, P. Worstell), pp. 801822. U.S. Govt. Printing Ofce, Washington, D.C. Bethoux, J.-P. and Pierre, C. (1999) Mediterranean functioning and sapropel formation: respective inuences of climate and hydrological changes in the Atlantic and the Mediterranean. Mar. Geol., 153, 2939. Bitterli, P. (1963) Aspects of the genesis of bituminous rock sequences. Geol. Mijnbouw, 42, 183201. Bouloubassi, I., Rullkotter, J. and Meyers, P.A. (1999) Origin and transformation of organic matter in Pliocene-Pleistocene Mediterranean sapropels: organic geochemical evidence. Mar. Geol., 157, 177197. Bradley, W.H. (1938) Mediterranean sediments and Pleistocene sea levels. Science, 88, 376379. Brass, G.W., Southam, J.R. and Peterson, W.H. (1982) Warm saline bottom water in the ancient ocean. Nature, 296, 620 623. Bray, E.E. and Evans, E.D. (1965) Vorkommen von Kohlenw asserstoffen in tonigen Muttergesteinen. Erdol-Kohle-ErgasPetrochemie, 18, 421424. Breheret, J.G. (1985) Sedimentology and Diagenesis of Organic-Matter from the Paquier Level, a Lowermost Albian Key-Bed of the Vocontian Basin. CR Acad. Sci. Paris, Serie II, 301, 11511156. Breheret, J.G. (1988) Episodes de sedimentation riches en ` matiere organique dans les marnes bleues dage Aptien et Albien de la partie pelagique du bassin vocontien. Bull. Geol. Soc. Fr., 8, 349356. von Buch, L. (1839) Uber den Jura in Deutschland. Druckerei der Koniglichen Akademie der Wissenschaften zu Berlin (F. Dummler in Kommission), Berlin, 87 pp. Calvert, S. (1987) Oceanographic controls on the accumulation of organic matter in marine sediments. In: Marine Petroleum Source Rocks (Eds J. Brooks and A.J. Fleet), Geol. Soc. London Spec. Publ., 26, pp. 137151. Blackwells, London. Calvert, S.E., Nielsen, B. and Fontugne, M.R. (1992) Evidence from nitrogen isotope ratios for enhanced productivity during formation of eastern Mediterranean sapropels. Nature, 359, 223225. Caneld, D.E. (1994) Factors inuencing organic carbon preservation in marine sediments. Chem. Geol., 114, 315329. van Cappellen, P. and Ingall, E.I. (1994) Benthic phosphorus regeneration, net primary production, and ocean anoxia: A model of the coupled marine biogeopchemical cycles of carbon and phosphorus. Paleoceanography, 9, 677692.

2009 The Authors. Journal compilation 2009 International Association of Sedimentologists, Sedimentology, 56, 247266

TethyanMediterranean sediments from Mesozoic black shales to sapropels

Emiliani, C. (1955) Pleistocene temperature variations in the Mediterranean. Quaternaria, 3, 8798. Eppley, R.W. and Peterson, B.J. (1979) Particulate organic matter ux and planktonic new production in the deep ocean. Nature, 282, 677680. Erba, E. and Tremolada, F. (2004) Nannofossil carbonate uxes during Early Cretaceous: phytoplankton response to nutrication episodes, atmospheric CO2 and anoxia. Paleoceanography, 19, doi: 10.1029/2003PA000884. Erba, E., Bartolini, A. and Larson, R.L. (2004) Valanginian Weissert oceanic anoxic event. Geol. Soc. Am. Bull., 32, 149152. Erbacher, J., Huber, B.T., Norris, R.D. and Markey, M. (2001) Increased thermohaline stratication as a possible cause for an ocean anoxic event in the Cretaceous period. Nature, 409, 325327. Fonselius, S.H. (1974) Phosphorus in Black Sea. In: The Black Sea. Geology, Chemistry and Biology (Eds E.T. Degens and D.A. Ross), pp. 144150. AAPG Memoir. AAPG, Tulsa, OK. Grocke, D.R., Hesselbo, S.P. and Jenkyns, H.C. (1999) Carbonisotope composition of Lower Cretaceous fossil wood: ocean-atmosphere chemistry and relation to sea-level change. Geology, 27, 155158. Hallam, A. (Ed) (1980) Black Shales. Bull. Geol. Soc. London, 137, 123124. Hallam, A. and Bradshaw, M.J. (1979) Bituminous shales and oolitic ironstones as indicators of transgressions and regressions. J. Geol. Soc. London, 136, 157164. Haq, B.U., Hardenbol, J. and Vail, P.R. (1987) Chronology of uctuating sealevels since the Triassic. Science, 235, 1156 1166. Haupt, B.J. and Seidov, D. (2001) Warm deep-water ocean conveyor during Cretaceous time. Geology, 29, 295298. Herbert, T. (1992) Paleomagnetic calibration of Milankovich cyclicity in Lower Cretaceous sediments. Earth Planet. Sci. Lett., 112, 1528. Herrle, J.O., Pross, J., Friedrich, O. and Hemleben, C. (2003) Short-term environmental changes in the Cretaceous Tethyan Ocean micropalaeontological evidence from the Early Albian Oceanic Anoxic Event 1b. Terra Nova, 15, 1419. Hesselbo, S.P., Grocke, D.R., Jenkyns, H.C., Bjerrum, C.J., Farrimond, P., Morgans Bell, H.S. and Green, O.R. (2000) Massive dissociation of gas hydrate during a Jurassic oceanic anoxic event. Nature, 406, 392395. Hilgen, F.J. (1991) Astronomical calibration of Gauss to Matuyama sapropels in the Mediterranean and implication for the Geomagnetic Polarity Time Scale. Earth Planet. Sci. Lett., 107, 226244. Hochuli, P.A., Menegatti, A.P., Weissert, H., Riva, A., Erba, E. and Premoli-Silva, I. (1999) Episodes of high productivity and cooling in the early Aptian Alpine Tethys. Geology, 27, 657660. Howell, M.W. and Thunell, R.C. (1992) Organic carbon accumulation in Bannock Basin: evaluating the role of productivity in the formation of eastern Mediterranean sapropels. Mar. Geol., 103, 461471. Hsu, K.J. (1976) Paleoceanography of the Mesozoic alpine Tethys. GSA Spec. Pap., 170, 44. Hsu, K.J. and Jenkyns, H.C. (Eds) (1974) Pelagic sediments: on land and under the sea. Int. Assoc. Sedimentol. Spec. Publ. 1, 447. Hsu, K.J. and Montadert, L. (Eds) (1978) Init. Repts. DSDP, 42A. Govt. Printing Ofce, Washington, DC. Jansa, L., Enos, P., Tucholke, B.E., Gradstein, F.M. and Sheridan, R.E. (1979) Mesozoic and Cenozoic sedimentary

263

formations in the North American Basin, western North Atlantic. In: Deep Drilling Results in the Atlantic Ocean: Continental Margins and Paleoenvironment. (Ed. M. Talwani), Maurice Ewing Series, 3, pp. 157. American Geophysical Union, Washington, DC. Jenkyns, H.C. (1980) Cretaceous anoxic events: from continents to oceans. J. Geol. Soc. London, 137, 171188. Jenkyns, H.C. (2003) Evidence for rapid climate change in the Mesozoic-Paleogene greenhouse world. Phil. Trans. R. Soc. London A, 361, 18851916. Jenkyns, H.C. and Clayton, C.J. (1986) Black shales and carbon isotopes in pelagic sediments from the Tethyan Lower Jurassic. Sedimentology, 33, 87106. Jenkyns, H.C., Grocke, D.R. and Hesselbo, S.P. (2001) Nitrogen isotope evidence for water mass denitrication during the early Toarcian (Jurassic) oceanic anoxic event. Paleoceanography, 16, 593603. Jenkyns, H.C., Jones, C.E., Grocke, D.R., Hesselbo, S.P. and Parkinson, D.N. (2002) Chemostratigraphy of the Jurassic System: applications, limitations and implications for palaeoceanography. J. Geol. Soc. London, 159, 351378. Jones, R.W. (1987) Organic facies. Adv. Petrol. Geochem., 2, 1 90. Jorissen, F.J. (1999) Benthic foraminiferal successions across Late Quaternary Mediterranean sapropels. Mar. Geol., 153, 91101. de Kaenel, E., Siesser, W.D. and Murat, A. (1999) Pleistocene calcareous nannofossil biostratigraphy and the western Mediterranean sapropels, Sites 974 to 977 and 979. In: Proc. ODP, Scientic Results (Eds R. Zahn, M. Comas and A. Klaus), Vol. 161, pp. 159183. Ocean Drilling Program, College Station, TX. Karl, D., Michaels, A., Bergman, B., Capone, D., Carpenter, E., Letelier, R., Lipschultz, F., Paerl, H., Sigman, D. and Stal, L. (2002) Dinitrogen xation in the worlds oceans. Biogeochemistry, 57/58, 4798. Kastens, K.A., Mascle, J., Auroux, C., Bonatti, E., Broglia, C., Channell, J., Curzi, P., Emeis, K.-C., Glagon, G., Hasegawa, S., Hieke, W., McCoy, F., McKenzie, J., Mascle, G., Mendelson, J., Muller, C., Rehault, J.-P., Robertson, A., Sartori, R., Sprovieri, R. and Torii, M. (1987) Proc. ODP: Initial Reports. Vol. 107. Ocean Drilling Program, College Station, TX, 1013 pp. Keller, J., Ryan, W.B.F., Ninkovich, D. and Altherr, R. (1978) Explosive volcanic activity in the Mediterranean over the last 200,000 yr as recorded in deep-sea sediments. Geol. Soc. Am. Bull., 89, 591604. Kemp, A.E., Pearce, R.B., Koizumi, I., Pike, J. and Rance, J. (1999) The role of mat-forming diatoms in the formation of Mediterranean sapropels. Nature, 398, 5761. Kidd, R.B., Cita, M.B. and Ryan, W.B.F. (1978) Stratigraphy of eastern Mediterranean sapropel sequences recovered during Leg 42A and their paleoenvironmental signicance. In: Init. Repts. DSDP (Eds K. Hsu and J.L. Montadert), Vol. 42, pp. 421443. U.S. Govt. Printing Ofce, Washington, DC. Klemme, H.D. and Ulmishek, G.F. (1991) Effective Petroleum Source Rocks of the World: Stratigraphic Distribution and Controlling Depositional Factors. AAPG Bull., 75, 1809 1851. Kroon, D., Alexander, I., Little, M., Lourens, L.J., Matthewson, A., Robertson, A.H.F. and Sakamoto, T. (1998) Oxygen isotope and sapropel stratigraphy in the eastern Mediterranean during the last 4 Million years (ODP Leg 160, Site 967 results). In: Proc. ODP, Scientic Results, 160 (Eds A.H.F.

2009 The Authors. Journal compilation 2009 International Association of Sedimentologists, Sedimentology, 56, 247266

264

K.-C. Emeis and H. Weissert

cated by accelerator mass spectrometry radiocarbon and geochemical evidence. Paleoceanography, 15, 336347. Meulenkamp, J.E., Driever, B.W.M., Jonkers, H.A., Spaak, P., Zachariasse, J.W. and van der Zwaan, G. (1979) Late Miocene-Pliocene climatic uctuations and marine cyclic sedimentation patterns. Annales Geologiques des Pays Helleniques, Hors Serie 11, 831842. Muller, P.J. and Suess, E. (1979) Productivity, sedimentation rate, and sedimentary organic carbon in the ocean I. Organic carbon preservation. Deep-Sea Res., 26A, 13471362. Myers, P.G., Haines, K. and Rohling, E.J. (1998) Modeling the paleocirculation of the Mediterranean: The last glacial maximum and the Holocene with emphasis on the formation of sapropel S1. Paleoceanography, 13, 586606. Neftel, A., Oeschger, H., Schwander, J., Stauffer, B. and Zumbrunn, R. (1982) Ice core sample measurements give atmospheric CO2 content during the past 40,000 yr. Nature, 295, 220223. Olausson, E. (1961) Studies of deep-sea cores. Reports of the Swedish Deep-Sea Expedition, 19471948, Vol. 8, pp. 353 391. Pancost, R.D., Crawford, N., Magness, S., Turner, A., Jenkyns, H.C. and Maxwell, J.R. (2004) Further evidence for the development of photic-zone euxinic conditions during Mesozoic ocean anoxic events. J. Geol. Soc. London, 161, 353364. Parker, F.L. (1958) Eastern Mediterranean foraminifera. Reports of the Swedish Deep Sea Expedition, 1947 217283 1948, 4, 217283. Passier, H.F., Bosch, H.-J., Nijenhuis, I.A., Lourens, L.J., Bottcher, M.E., Leenders, A., Sinninghe Damste, J.S., de Lange, G.J. and de Leeuw, J.W. (1999) Sulphic Mediterranean surface waters during Pliocene sapropel formation. Nature, 397, 146149. Pedersen, T.F. and Calvert, S.E. (1990) Anoxia vs. productivity: what controls the formation of organic-carbon-rich sediments and sedimentary rocks? AAPG Bull., 74, 454466. Pitman, W.C. III (1978) Relationship between eustacy and stratigraphic sequences of passive margins. Geol. Soc. Am. Bull., 89, 13891403. Potonie, H. (1904) Uber Faulschlamm-(Sapropel)-Gesteine. Sitz. Gesell. nat. V. Berlin, pp., 243245. Rau, G.H., Arthur, M.A. and Dean, W.E. (1987) 15N/14N variations in Cretaceaous Atlantic sedimentary sequences: implication for past changes in marine nitrogen biogeochemistry. Earth Planet. Sci. Lett., 82, 269279. Reboulet, S., Mattioli, E., Pittet, B., Baudin, F., Olivero, D. and Proux, O. (2003) Ammonoid and nannoplankton abundance in Valanginian (early Cretaceous) limestone-marl successions from the southeast France Basin: carbonate dilution or productivity? Palaeogeogr., Paleoclimatol., Palaeoecol., 201, 113139. Rohling, E.J. (1994) Review and new aspects concerning the formation of eastern Mediterranean sapropels. Mar. Geol., 122, 128. Rohling, E.J. and Hilgen, F.J. (1991) The eastern Mediterranean climate at times of sapropel formation: a review. Geol. Mijnbow, 70, 253264. Rohling, E.J., Jorissen, F.J. and de Stigter, H.C. (1997) 200 year interuption of Holocene sapropel formation in the Adriatic Sea. Journ. Micropalaeontology, 16, 97108. Rohling, E.J., Cane, T.R., Cooke, S., Sprovieri, M., Bouloubassi, I., Emeis, K.-C., Schiebel, R., Kroon, D., Jorissen, F.J., Lorre, A. and Kemp, A.E.S. (2002) African monsoon vari-

Robertson, K.-C. Emeis, C. Richter and A. Camerlenghi), pp. 181189. Ocean Drilling Program, College Station, TX. Kuhnt, W., Luderer, F., Nederbragt, S., Thurow, J. and Wagner, T. (2005) Orbital-scale record of the late CenomanianTuronian oceanic anoxic event (OAE-2) in the Tarfaya Basin (Morocco). Int. J. Earth Sci., 94, 147159. Kullenberg, B. (1952) On the salinity of water contained in marine sediments. Meddelanden fran Oceanograska In stitutet i Goteborg, 21, 138. Kuypers, M.M.M., Pancost, R.D., Nijenhuis, I.A. and Sinnin ghe Damste, J.S. (2002) Enhanced productvity led to increased organic carbon burial in the euxinic North Atlantic basin during the late Cenomanian oceanic anoxic event. Paleoceanography, 17, 31 to 313. Kuypers, M.M.M., Van Breugel, Y., Schouten, S., Erba, E. and Sinninghe Damste, J.S. (2004) N2-xing cyanobacteria supplied nutrient N for Cretaceous oceanic anoxic events. Geology, 32, 853856. Kvenvolden, K.A. (1988) Methane hydrate a major reservoir of carbon in the shallow geosphere. Chem. Geol., 71, 4151. Larson, R.L. (1991) Latest pulse of the Earth: evidence for a mid Cretaceous super plume. Geology, 19, 547550. Larson, R.L. and Erba, E. (1999) Onset of the mid-Cretaceous greenhouse in the Barremian-Aptian: igneous events and the biological, sedimentary, and geochemical responses. Paleoceanography, 14, 663678. Lini, A., Weissert, H. and Erba, E. (1992) The Valanginian Carbon Isotope Event a 1st episode of greenhouse climate conditions during the Cretaceous. Terra Nova, 4, 374384. Lourens, L.J. (2004) Revised tuning of Ocean Drilling Program Site 964 and KC01B (Mediterranean) and implications for the d18O, tephra, calcareous nannofossil, and geomagnetic reversal chronologies of the past 11 Myr. Paleoceanography, 19, doi:10.1029/2003PA000997. Lourens, L.J., Wehausen, R. and Brumsack, H.-J. (2001) Geological constraints on tidal dissipation and and dynamical ellipticity of the Earth over the past three million years. Nature, 409, 10291032. Lourens, L.J., Hilgen, F.J., Laskar, J., Shackleton, N.J. and Wilson, D. (2004) The Neogene Period. In: A Geologic Time Scale (Eds F.M. Gradstein, J.G. Ogg and A.G. Smith), pp. 409440. Cambridge University Press, Cambridge. Masson, V., Braconnot, P., Jouzel, J., de Noblet, N., Cheddadi, R. andMarchal,O.(2000)Simulationof intensemonsoons under glacialconditions.Geophys.Res.Lett.,27,17471750. Matthiesen, S. and Haines, K. (2003) A hydraulic box model study of the Mediterranean response to postglacial sea-level rise. Paleoceanography, 18, 81 812. McCoy, F.W. (1974) Late Quaternary Sedimentation in the Eastern Mediterranean Sea, Harvard University, Cambridge, MA, 132 pp. Menegatti, A.P., Weissert, H., Brown, R.S., Tyson, R.V., Farrimond, P., Strasser, A. and Caron, M. (1998) High-resolution delta C-13 stratigraphy through the early Aptian Livello Selli of the Alpine Tethys. Paleoceanography, 13, 530545. Menzel, D., Hopmans, E.C., van Bergen, P.F., de Leeuw, J.W. and Sinninghe Damste, J.S. (2002) Development of photic zone euxinia in the eastern Mediterranean Basin during deposition of Pliocene sapropels. Mar. Geol., 189, 215226. Mercone, D., Thomson, J., Croudace, I.W., Siani, G., Paterne, M. and Troelstra, S.R. (2000) Duration of S1, the most recent sapropel in the eastern Mediterranean Sea, as indi-

2009 The Authors. Journal compilation 2009 International Association of Sedimentologists, Sedimentology, 56, 247266

TethyanMediterranean sediments from Mesozoic black shales to sapropels

ability during the previous interglacial maximum. Earth Planet. Sci. Lett., 202, 6175. Rossignol-Strick, M. (1983) African monsoons, an immediate climate response to orbital insolation. Nature, 304, 4649. Rossignol-Strick, M. (1985) Mediterranean Quaternary sapropels, an immediate response of the African Monsoon to variation of insolation. Palaeogeogr. Palaeoclimatol. Palaeoecol., 49, 237263. Ryan, W.B.F. (1972) Stratigraphy of Late Quaternary sediments in the eastern Mediterranean. In: The Mediterranean Sea: a Natural Sedimentation Laboratory (Ed. D.J. Stanley), pp. 149169. Dowden, Hutchinson and Ross, Stroudsberg, PA. Ryan, W.B.F. and Cita, M.B. (1977) Ignorance concerning episodes of oceanwide stagnation. Mar. Geol., 23, 197215. Ryan, W.B.F. and Hsu, K.J. (Eds) (1973) Initial Repts. DSDP, 13. Govt. Printing Ofce, Washington, DC. Sachs, J.P. and Repeta, D.J. (1999) Oligotrophy and nitrogen xation during Eastern Mediterranean sapropel events. Science, 286, 24852488. Schlanger, S.O. and Jenkyns, H.C. (1976) Cretaceous anoxic events: causes and consequences. Geol. Mijnbouw, 55, 179 184. Schmiedl, G., Mitschele, A., Beck, S., Emeis, K.-C., Hemleben, C., Schulz, H., Sperling, M. and Weldeab, S. (2003) Benthic foraminiferal record of ecosystem variability in the eastern Mediterranean Sea during the times of sapropel S5 and S6. Palaeogeogr. Palaeoclimatol. Palaeoecol., 190, 139164. Scholle, P.A. and Arthur, M.A. (1980) Carbon isotope uctuations in Cretaceous pelagic limestones: Potential stratigraphic and petroleum exploration tool. Amer. Assoc. Petrol. Geol. Bull., 64 1, 6787. Schrader, H. and Matherne, A. (1981) Sapropel formation in the eastern Mediterranean sea: evidence from preserved opal assemblages. Micropaleontology, 27, 191203. Selli, R., Accorsi, C.A., Mazzanti, M., Bertolani Marchetti, D., Bigazzi, G., Bonadonna, F.G., Borsetti, A.M., Cati, F., Colalongo, M.L., dOnofrio, S., Landini, W., Menesini, E., Mezzetti, R., Pasini, G., Savelli, C. and Tampieri, R. (1977) The Vrica section (Calabria, Italy). A potential Neogene/ Quaternary stratotype. Giorn. Geol., 42, 181204. Slomp, C.P., Thomson, J. and deLange, G.J. (2002) Enhanced regeneration of phosphorus during formation of the most recent eastern Mediterranean sapropel (S1). Geochim. Cosmochim. Acta, 66, 11711184. Spears, D.A. (1980) Towards a classication of shales. J. Geol. Soc. London, 137, 125129. Stratford, K., Williams, R.G. and Myers, P.G. (2000) Impact of the circulation on sapropel formation in the eastern Mediterranean. Global Biogeochem. Cycles, 14, 683695. Strohle, K. and Krom, M. (1997) Evidence for the evolution of an oxygen minimum layer at the beginning of S-l sapropel deposition in the eastern Mediterranean. Mar. Geol., 140, 231236. Struck, U., Emeis, K.-C., Rau, G.H., Voss, M. and Krom, M. (2001) Biological productivity during sapropel S5 formation in the eastern Mediterranean Sea evidence from stable isotopes of nitrogen and carbon. Geochim. Cosmochim. Acta, 65, 32413258. Suess, E. (1980) Organic carbon ux in the oceans: relation to surface productivity and oxygen utilization. Nature, 288, 260263. Svensen, H., Planke, S., Malthe-Sorenssen, A., Jamtveit, B., Myklebust, R., Eidem, T.R. and Rey, S.S. (2004) Release of

265

methane from a volcanic basin as a mechanism for initial Eocene global warming. Nature, 429, 542545. Thiede, J. and Van Andel, T.H. (1977) The paleoenvironment of anaerobic sediments in the late Mesozoic south Atlantic Ocean. Earth Planet. Sci.e Lett.s, 33, 301309. Tsikos, H., Jenkyns, H.C., Walsworth-Bell, B., Petrizzo, M.R., Forster, A., Kolonic, S., Erba, E., Silva, I.P., Baas, M., Wagner, T. and Sinninghe Damste, J.S. (2004) Carbonisotope stratigraphy recorded by the Cenomanian-Turonian Oceanic Anoxic Event: correlation and implications based on three key localities. J. Geol. Soc. London, 161, 711719. Tuenter, E. (2004) Modeling orbital induced variations in circum-Mediterranean climate. PhD dissertation, Universiteit Utrecht, Utrecht, 144 pp. Tyrrell, T. (1999) The relative inuences of nitrogen and phosphorus on oceanic primary production. Nature, 400, 525531. Veizer, J., Ala, D., Azmy, K., Bruckschen, P., Bruhn, F., Buhl, D., Carden, G., Diener, A., Ebneth, S., Goddris, Y., Jasper, T., Korte, C., Pawellek, F., Podlaha, O.G. and Strauss, H. (1999) 87Sr/86Sr, d13C and d18O evolution of Phanerozoic seawater. Chem. Geol., 161, 5988. Vergnaud-Grazzini, C., Ryan, W.B.F. and Cita, M.B. (1977) Stable isotope fractionation, climatic change and episodic stagnation in the eastern Mediterranean during the Late Quaternary. Mar. Micropaleontol., 2, 353370. Vine, J.D. and Tourtelot, E.B. (1970) Geochemistry of black shale deposits a summary report. Econ. Geol., 65, 253 272. Voigt, S. (2000) Cenomanian-Turonian composite delta C-13 curve for Western and Central Europe: the role of organic and inorganic carbon uxes. Palaeogeogr. Palaeoclimatol. Palaeoecol., 160, 91104. Wagner, T., Sinninghe Damste, J.S., Hofmann, P. and Beckmann, B. (2004) Euxinia and primary production in Late Cretaceous eastern equatorial Atlantic surface waters fostered orbitally driven formation of marine black shales. Paleoceanography, 19, doi: 10.1029/2003PA000898. Wallmann, K. (2003) Feedbacks between oceanic redox states and marine productivity: a model perspective focused on benthic phosphorus cycling. Global Biogeochem. Cycles, 17/ 3, 117. Weissert, H. (1981) The environment of deposition of black shales in the Early Cretaceous: an ongoing controversy. In: The Deep Sea Drilling Project: a Decade of Progress (Eds J.E. Warme, R.G. Douglas and E.L. Winterer), Soc. Econ. Paleo. Min. Spec. Publ., 32, 547560. Weissert, H. (2000) Global change deciphering methanes ngerprint. Nature, 406, 356357. Weissert, H. and Erba, E. (2004) Volcanism, CO2 and paleoclimate: a Late JurassicEarly Cretaceous carbon and oxygen isotope record. J. Geol. Soc. London, 161, 695702. Weissert, H., McKenzie, J.A. and Hochuli, P. (1979) Cyclic anoxic events in the Early Cretaceous Tethys Ocean. Geology, 7, 147151. Weissert, H., McKenzie, J.A. and Channell, J.E.T. (1985) Natural variations in the carbon cycle during the Early Cretaceous. In: The Carbon Cycle and Atmospheric CO2: Natural Variations Archean to the Present (Eds E.T. Sundquist and W.S. Broecker) Geophys. Monogr. 32, 531545. Weissert, H., Lini, A., Follmi, K.B. and Kuhn, O. (1998) Correlation of Early Cretaceous carbon isotope stratigraphy and platform drowning events: a possible link? Palaeogeogr. Palaeoclimatol. Palaeoecol., 137, 189203.

2009 The Authors. Journal compilation 2009 International Association of Sedimentologists, Sedimentology, 56, 247266

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K.-C. Emeis and H. Weissert

Wissler, L., Funk, H. and Weissert, H. (2003) Response of Early Cretaceous carbonate platforms to changes in atmospheric carbon dioxide levels. Palaeogeogr. Palaeoclimatol. Palaeoecol., 200, 187205.

Weldeab, S., Emeis, K.-C., Hemleben, C., Schmiedl, G. and Schulz, H. (2003) Spatial productivity variations during formation of sapropels S5 and S6 in the Mediterranean Sea: Evidence from Ba concentrations. Palaeogeogr. Palaeoclimatol. Palaeoecol., 191, 169190. Welte, D.H. (1972) Petroleum exploration and organic geochemistry. J. Geoch. Explor., 1, 117136. Wezel, F.C. (1985) Facies anossiche ed episodi geotettonici globali. Giornale di Geologia, Serie 3a, 47.

Manuscript received 1 February 2008; revision accepted 26 August 2008

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