GEOLOGICA ULTRAIECTINA Mededelingen van de Faculteit Aardwetenschappen Universiteit Utrecht No. 202 Fluxes, diagenesis and preservation of recent and Holocene sediments in the eastern Mediterranean Arrian Rutten Cover picture Pigment concentrations in Mediterranean surface water measured by the Coastal Zone Colour Scanner, May 1980. Light colours indicate high pigment concentrations, darker colours low concentrations. Data are courtesy of NASA/GSFC. ISBN 90-5744-059-8 Fluxes, diagenesis and preservation of recent and Holocene sediments in the eastern Mediterranean Fluxen, diagenese en preservatie van recente en Holocene sedimenten in de oostelijke Middellandse Zee. (met een samenvatting in het Nederlands) PROEFSCHRIFT TER VERKRIJGING VAN DE GRAAD VAN DOCTOR AAN DE UNIVERSITEIT UTRECHT OP GEZAG VAN DE RECTOR MAGNIFICUS, PROF. DR. W.H. GISPEN, INGEVOLGE HET BESLUIT VAN HET COLLEGE VOOR PROMOTIES IN HET OPENBAAR TE VERDEDIGEN OP WOENSDAG 18 APRIL 2001 DES MIDDAGS OM 14.30 UUR DOOR ARRIAN RUTTEN geboren op 21 september 1972, te Dongen Promotor: Prof. Dr. C.H. van der Weijden Department of Geochemistry, Utrecht University, Utrecht, The Netherlands Co-promotor: Dr. G.J. de Lange Department of Geochemistry, Utrecht University, Utrecht, The Netherlands The research described in this thesis was carried out at the Department of Geochemistry, Institute of Palaeo-environments and Palaeoclimate Utrecht (IPPU), Utrecht University, Budapestlaan 4, PO Box 80021, 3508 TA Utrecht, The Netherlands. This study was supported by MARFLUX (MAST1-90022C), PALAEOFLUX (MAS2-CT93- 0051) and SAP (MAS3-CT97-0137) European programmes. “In the beginning the universe was created. This has made a lot of people very angry and been widely regarded as a bad move.” Douglas Adams – The restaurant at the end of the universe 7 Contents Chapter 1 Introduction and summary 9 Chapter 2 Recent terrestrial and carbonate fluxes in the pelagic eastern 15 Mediterranean; a comparison between sediment trap and surface sediment Chapter 3 Present-day coccolith fluxes recorded in central eastern 39 Mediterranean sediment traps and surface sediments Chapter 4 Deposition of sapropel S1 sediments in oxic pelagic and 65 anoxic brine environments in the eastern Mediterranean; differences in diagenesis and preservation Chapter 5 Sequential extraction of iron, manganese and related trace 85 elements, tested on natural minerals and applied to eastern Mediterranean sediments Chapter 6 A novel selective extraction for barite from marine sediments 113 Chapter 7 Sequential extraction of aragonite, calcite and dolomite from 129 eastern Mediterranean sediments References 147 Inleiding en samenvatting 163 Acknowledgements 171 Curriculum Vitae 173 9 Chapter 1 Introduction and summary 1.1 Setting The Mediterranean Sea is a semi-enclosed basin, bordered in the south by the African continent and in the north by Eurasia. The only connection to the world ocean is via the shallow Strait of Gibraltar. The Mediterranean Sea itself is divided into two main parts, the western and the eastern Mediterranean (Fig. 1.1), which are separated by the sill in the Strait of Sicily. At present, evaporation exceeds precipitation, which results in an anti-estuarine circulation; nutrient-depleted Atlantic surface water flows into the Mediterranean, and nutrient-enriched Mediterranean Intermediate Water flows out. Due to this export of nutrients, the present-day Mediterranean Sea can be considered a nutrient desert. Overall organic matter production is very low compared to the world ocean, and 85% of the primary production in the eastern Mediterranean flows into the microbial foodweb (Turley, 1997). Phytoplankton populations are dominated by picoplankton, with the bacterial biomass constituting about 50% of total algal biomass (Robarts et al., 1996). Presently, eastern Mediterranean sediments consist mainly of terrestrial and carbonate fractions, whereas organic matter and opal contents are very low. Figure 1.1 Location of the sediment trap deployment (ST) and the boxcores of which results are discussed in this thesis. 10 Chapter 1 1.2 Sapropel formation The 1948 Swedish Deep-Sea Expedition brought the first evidence for the existence of intervals with organic-rich sediments in the eastern Mediterranean (Kullenberg, 1952). In subsequent years, the cyclic occurrence of such organic-rich sediments within otherwise organic-poor intervals has been identified, in sediment cores (e.g. Cita et al., 1977; Kidd et al., 1978; Calvert, 1983; Pruysers et al., 1991; Van Santvoort et al., 1997; Nijenhuis et al., 1999) as well as in land sections (e.g. Sprovieri et al., 1986; De Visser et al., 1989; Van der Weijden et al., 1993; Van Os et al., 1994; Nijenhuis et al., 1996; Schenau et al., 1999). These organic-rich units, which can be dated back to the Miocene, have been named sapropels, for which Kidd et al. (1978) proposed the following definition: “discrete layers, greater than 1 cm in thickness, set in open marine sediment and containing greater than 2% organic carbon”. However, this definition is rather restrictive, and for that reason Van Santvoort et al. (1996) proposed the following refinement: “discrete sediment layers with an organic carbon content that is significantly higher than that of the surrounding hemipelagic sediment and being deposited in an open marine environment”. The cyclicity in eastern Mediterranean sediments has been related to variations in the eccentricity of the Earth’s orbit and in the tilt (obliquity) and precession of the Earth’s axis (e.g. Rossignol-Strick, 1983, 1985; Hilgen, 1991; Lourens, 1994; Hilgen et al., 1995). Sapropel formation is dominated by the precession cyclicity (~23 kyrs), with sapropel deposition occurring when Northern Hemisphere insolation is at its maximum caused by a minimum in the Earth’s solar precession. There is growing evidence that sapropels were formed during periods of wetter climatic conditions at times of the precession minimum (Rossignol-Strick et al., 1982; Rossignol-Strick, 1985; Kallel et al., 1997). These conditions caused enhanced river run-off and nutrient supply into the Mediterranean basin. It is, however, still a matter of debate what caused the high organic matter content of sapropels. The increased fresh water input may have resulted in the development of a low-salinity surface layer, which in turn reduced deep-water circulation. A stagnating water column may have led to anoxic bottom water conditions and a better preservation of organic matter (Olausson, 1961; Cita et al., 1977; Nolet and Corliss, 1990). Alternatively, it has been proposed that an increase in marine productivity rather than enhanced preservation of organic matter was the driving mechanism behind sapropel formation (Calvert, 1983; Calvert et al., 1992). Rohling and Gieskes (1989) combined both scenarios and argued that a distinct Deep Chlorophyll Maximum may have developed within the euphotic zone, thereby enhancing primary productivity. 1.3 Brine basins In 1983, a deep basin filled with salt-saturated seawater was discovered in the eastern Mediterranean during the 1983 expedition of R.V. Tyro (De Lange and Ten Haven, 1983; Jongsma et al., 1983). A year later, another such basin was found by R.V. Bannock (Scientific staff of Cruise Bannock 1984-2, 1985). These brine basins, named after the ships that discovered them (Tyro Basin and Bannock Basin respectively), have persisting anoxic conditions due to the high density of the seawater in these basins, preventing ventilation. In Introduction and summary 11 the Tyro Basin area, two formerly brine-filled basins, Kretheus and Poseidon Basins, were also discovered. In the mid-1990's, again three brine basins were found: Urania, Atalante and Discovery Basins (MEDRIFF Consortium, 1995). These brine basins offer a unique opportunity to study contemporary oxic and anoxic sedimentation. The occurrence of perfectly preserved radiolarians and of sulphate reduction in anoxic brine sediments but not in contemporaneous oxic pelagic sediments in the eastern Mediterranean suggests that — assuming similar inputs to these two types of sediment — biogenic silica and reactive organic matter are preferentially preserved in these brine sediments (Björklund and De Ruiter, 1987; Troelstra, 1987; Aghib, 1996; Henneke et al., 1997). C-org (wt%) Ba (ppm) Fe/Al (g/g) Mn/Al (g/g) V/Al (mg/g) 0 1 2 3 0 600 1200 0.4 0.8 1.2 0.0 0.2 0.4 0 4 8 0 ) m 10 c ( h t p e 20 d 30 Figure 1.2 Typical distributions of organic carbon, Ba, and the redox-sensitive elements Fe, Mn and V in Holocene eastern Mediterranean sediments. The metal contents are divided by Al to correct for carbonate dilution. The dark-grey area indicates the visible sapropel (its sediment is black-green in colour), the light-grey area the oxidised sapropel interval (its sediment is red-brown in colour). The shown results are from boxcore ABC26. 1.4 Diagenesis of sapropel S1 After deposition sapropels undergo significant chemical alteration (diagenesis). It has been observed that organic matter profiles in Holocene sediments may vary significantly over the eastern Mediterranean basin, but that metal distributions are rather alike (e.g. Pruysers et al., 1991, 1993; Higgs et al., 1994; Thomson et al., 1995, 1999; Van Santvoort et al., 1996; see Fig. 1.2). These features resemble those found for organic-enriched turbidites in the Madeira Abyssal Plain (De Lange et al., 1989), which experienced diagenesis by a downward- moving oxidation front (e.g. Colley et al., 1984; Thomson et al., 1984, 1987; Wilson et al., 1985, 1986; Jarvis and Higgs, 1987). This has led to the hypothesis that sapropels, which are intercalated between organic-poor sediments, have been subject to a similar oxidation process, removing significant amounts of organic matter and other reduced species such as pyrite from the top of the sapropel and redistributing metal contents in the sediment column. Most investigations have focussed on the most recent sapropel (S1), which was deposited in the Holocene. This sapropel contains the most fresh geochemical evidence of its 12 Chapter 1 diagenesis and radiocarbon dating can be applied to it (e.g.