Biogeochemical investigation of cold seep sediments in the Eastern Mediterranean Sea

Cold seep ecosystems are highly productive, fragmented ecosystems of the deep-sea floor. They form worldwide where methane reaches the surface seafloor, and are characterized by rich chemosynthetic communities fueled by the microbial utilization of hydrocarbons. Here we investigated with in situ (benthic chamber, microprofiler) and ex situ (pore water constituents, turnover rates of sulfate and methane, prokaryote abundance) techniques reduced sites from three different seep ecosystems in the Eastern Mediterranean deep-sea. At all three cold seep systems, the Amon Mud Volcano, Amsterdam Mud Volcano and the Nile Deep Sea Fan Pockmark area, we observed and sampled patches of highly reduced, methane-seeping sulfidic sediments which were separated by tens to hundreds of (kilo)meters with non-reduced oxygenated seafloor areas. All investigated seep sites were characterized by gassy, sulfidic sediments of blackish color, of which some were overgrown with thiotrophic bacterial mats. Fluxes of methane and oxygen, as well as sulfate reduction rates varied between the different sites.

Sulfur concentrations and isotope ratios in sediments from Kiel Bay, western Baltic Sea

The isotope-ratios of sulfur-components in several sedimentologically different cores of recent marine sediments from Kiel Bay (Baltic Sea) were investigated. In addition, quantitative determinations were made on total sulfur, sulfate, sulfide, chloride, organic carbon, iron and watercontent in the sediment or in the pore-water solution. The investigations gave the following results: 1. The sulfur in the sediment (about 0.3 -2 % of the dry sample) was for the most part introduced into the sediment after sedimentation. This confirms the results of Kaplan et al. (1963, doi:10.1016/0016-7037(63)90074-7). The yield of Sulfur from organic material is very small (in our samples about 5-10% of the total sulfur in the sediment). 2. The sulfur bound in the sediment is taken from the sulfate of the interstitial water. During normal sedimentation, the exchange of sulfate by diffusion significant for changes in the sulfur-content goes down to a sediment depth of 4-6 cm. In this way the sulfate consumed by reduction and formation of sulfide or pyrite is mostly replaced. The uppermost layer of the sediment is an partly open system for the sulfur. The diagenesis of the sulfur is allochemical. 3. The isotope-values of the sediment-sulfur are largely influenced by the sulfur coming into the sediment by diffusion and being bound by bacteriological reduction. Due to the prevailing reduction of 32S and reverse-diffusion of sulfate into the open sea-water, an 32S enrichment takes place in the uppermost layer of the sediment. delta34S-values in the sediment range between -15 and -35 ? while seawater-sulfate has +20 ?. No relationship could be established between sedimentological or chemical changes and isotope-ratios. In the cores, successive sandy and clayly layers showed no change in the delta-values. The sedimentation rate, however, seems to influence isotope-ratios. In one core with low sedimentationrates the delta34S-values varied between -29 and -33 ?, while cores with higher sedimentationrates showed values between -17 and -24 ?. 4. As sediment depth increases, the pore-water sulfate shows decreasing concentrations (in a depth of 30-40 cm we found between 20 and 70 % of the seawater-values), and increasing delta 34S-values (in one case reaching more than +60 ?). The concentration of sulfide in the pore-water increases with sediment-depth (reaching 80 mg S/l in one case). The (delta34S-values of the pore-water-sulfide in all cores show increases paralleling the sulfate sulfur, with a nearly constant delta-distance of 50-60 ? in all cores. This seems to confirm the genetic relationship between the two components.

Petrographic description and mineral composition of ODP Site 161-975 sediments

Ocean Drilling Program Site 975 is located near the base of the Menorca Rise in the South Balearic Basin of the western Mediterranean Sea. Coring at this site penetrated the Pliocene/Miocene boundary and recovered a sequence of sediments that represent the final stages of salt deposition and the transition from evaporitic to open marine conditions at the end of the Miocene (Messinian). Detailed petrographic observations and bulk mineralogical analyses by X-ray diffraction form the basis for preliminary interpretations of depositional environments for this section. Gypsum is thought to have been deposited in an evaporating basin below wave base. Cycles consisting of a clay layer overlain by gypsiferous chalk, laminated gypsum, and finally pinch-and-swell gypsum suggest upsection increases in salinity. The gypsum section is overlain by two exotic sand layers thought to mark events of fresher water (marine or meteoric) inflow to the basin. Gypsum deposition terminated and was replaced by inorganic precipitation of micritic calcite with periodic, variable dilution by fine-grained terrigenous sediment. The micritic sediments have fine, slightly wavy, laminations indicating either an algal/microbial mat origin, or varve-like fluctuations in deposition, perhaps in a deep basin. The Pliocene/Miocene boundary falls within an interval of banded micritic silty clays that reflect the final environmental fluctuations during the transition to the open marine conditions of the Pliocene.

Grain size percentiles and Mk values of coastal sediments from Schleswig Holstein, western Baltic Sea

In einer Fülle sedimentpetrographischer Arbeiten wird versucht, aus der Korngrößenverteilung und der Mineralzusammensetzung von Sanden Schlüsse auf ihre Herkunft, ihre Transportrichtung oder ihr Ablagerungsmilieu abzuleiten, die für die Lösung geologischer und ebenso auch wasserbaulicher Probleme nötig sind. Diese Literatur steckt noch voller Widersprüche und Fehlschlüsse. In der vorliegenden Arbeit wird daher versucht, den Mechanismus des Sandtransports vom Grundsätzlichen her besser verständlich zu machen. Das geschieht anhand zweier ausgewählter und eingehend untersuchter Beispiele aus dem Küstenbereich der westlichen Ostsee unter Einbeziehung der Erfahrungen an vielen Vergleichsproben aus verschiedensten Sedimentationsräumen. Unentbehrlich für das Verständnis der transportbedingten Veränderungen an den Sanden ist das sog. 'Äquivalenzprinzip' (Abschnitt 2). Es stellt fest, daß es in einem von einer Strömung transportierten Sediment immer Körner zwar verschiedener Korngröße, aber auch entsprechend verschiedener Dichte und/oder Kornform gibt, die miteinander transportiert und abgelagert werden, weil unter den herrschenden hydraulischen Bedingungen diese Eigenschaften einander voll kompensieren. In Abschnitt 3 wird kurz die von Rittenhouse angegebene Methode geschildert, mit der man an natürlichen Sedimenten unter der sehr allgemein gehaltenen 'Äquivalenzbedingung' gleicher Transportierbarkeit bestimmen kann, welches Korngrößenverhältnis ein bestimmtes Verhältnis der Dichten kompensieren kann. Die von Rittenhouse am Beispiel von Flußsanden gefundene Funktion zwischen der Dichte der Körner und ihrem Äquivalenzverhältnis gegen Quarzkörner wird hier als erste Näherung auch für die Transportverhältnisse von Strandsanden zugrunde gelegt. In Abschnitt 6 wird gezeigt, daß das auch gerechtfertigt ist. In Abschnitt 4 wird eine allgemein brauchbare Methode abgeleitet, mit der man nicht nur unter stark vereinfachenden Annahmen, sondern auch an Sanden mit realen, stets komplexen Korn-größenverteilungen die Folgen des Äquivalenzprinzips für die Verteilung von Mineralen verschiedener Dichte berechnen kann. Für jede Serie von Sanden, deren Korngrößenverteilungen entlang des Transportweges eine bestimmte, von den Transportbedingungen abhängige Entwicklung durchmachen, ergibt sich damit eine Kurvenschar, die beschreibt, wie sich die Mengen von Mineralien mit verschiedenen Dichten in den einzelnen Korngrößenklassen dabei ändern müßten, vorausgesetzt, daß sie im gesamten Korngrößenbereich gleich verfügbar wären. Diese Kurvenschar ist die 'Charakteristik' des betreffenden Transportfalles. Durch den Vergleich zwischen den nach der Charakteristik in den einzelnen Klassen zu erwartenden Mineralmengen mit den in dem betrachteten Transportfall tatsächlich gefundenen läßt sich deren relative, d. h. auf die Menge des Quarzes bezogene 'Verfügbarkeit' berechnen. Sie wird durch die sog. 'hydraulischen Verhältnisse' (Rittenhouse) ausgedrückt, die im Gegensatz zu den 'Klassenverhältnissen' von der Korngrößensonderung beim Transport unabhängig und nur von der Zusammensetzung des Ausgangsmaterials bestimmt sind, solange beim Transport allein das Äquivalenzprinzip wirksam ist. In den untersuchten Fällen von Sandtransport an zwei Strandabschnitten der westlichen Ostsee (Abschnitt 5) zeigte dieser Vergleich (Abschnitt 6), daß die beobachtete Verteilung von Schwermineralen nicht allein durch Transportsonderung unter Gültigkeit des Äquivalenzprinzips erklärt werden kann, sondern daß dabei offenbar auch mechanische Zerkleinerung der Körner während des Transports mitgewirkt haben muß. Nur ein solcher, von der Transportsonderung unabhängiger Effekt kann als Transportrichtungs-Kriterium benutzt werden, wenn die Entwicklung der Korngrößenverteilungen allein keine Entscheidung erlaubt. Wie die Beispiele zeigen, läßt sich Klarheit über die bisher noch sehr umstrittene Frage nach dem Ausmaß der transportbedingten mechanischen Zerkleinerung von Sandkörnern nur gewannen, wenn in Zukunft versucht wird, bei der Bearbeitung natürlicher Beispiele den Einfluß der stets vorhandenen Transportsonderung auf Veränderungen des Mineralbestandes unter Anwendung des Äquivalenzprinzips rechnerisch auszuschalten. Über dieses wesentlichste Ergebnis hinaus erlauben die dargestellten Zusammenhänge auch eine kritische Stellungnahme zu den oben erwähnten allgemeinen Problemen und führen zu methodischen und sachlichen Verbesserungsvorschlägen für weitere Untersuchungen an klastischen Sedimenten.

Stable carbon and oxygen isotopes from samples of the Anaximander seamounts in the eastern Mediterranean Sea

Porous seep-carbonates are exposed at mud volcanoes in the eastern Mediterranean Sea. The 13C-depleted aragonitic carbonates formed as a consequence of the anaerobic oxidation of methane in a shallow sub-surface environment. Besides the macroscopically visible cavernous fabric, extensive carbonate corrosion was revealed by detailed analysis. After erosion of the background sediments, the carbonates became exposed to oxygenated bottom waters that are periodically influenced by the release of methane and upward diffusion of hydrogen sulphide. We suggest that carbonate corrosion resulted from acidity locally produced by aerobic oxidation of methane and hydrogen sulphide in the otherwise, with respect to aragonite, oversaturated bottom waters. Although it remains to be tested whether the mechanisms of carbonate dissolution suggested herein are valid, this study reveals that a better estimate of the significance of corrosion is required to assess the amount of methane-derived carbon that is permanently fixed in seep-carbonates.

Stable isotope composition of Holocene benthic foraminifers from the Eastern Mediterranean Sea

Temporal and regional changes in paleoproductivity and paleoceanography in the eastern Mediterranean Sea during the past 12 kyr were reconstructed on the basis of the stable oxygen and carbon isotope composition of the epibenthic Planulina ariminensis and the shallow endobenthic Uvigerina mediterranea from three sediment cores of the Aegean Sea and Levantine Basin. The Younger Dryas is characterized by high d18O values, indicating enhanced salinities and low temperatures of deep water masses at all investigated sites. With the onset of the Holocene, d18O records show a continuous decrease towards the onset of sapropel S1 formation, mainly caused by a freshening and warming of surface waters at deep water formation sites. In the middle and late Holocene, the similarity of d18O values from the southern Aegean Sea and Levantine Basin suggests the influence of isotopically identical deep water masses. By contrast, slightly higher d18O values are observed the northern Aegean Sea, which probably point to lower temperatures of North Aegean deep waters. The epifaunal d13C records reveal clear changes in sources and residence times of eastern Mediterranean deep waters associated with period of S1 formation. Available data for the early and late phase of sapropel S1 formation and for the interruption around 8.2 kyr display drops by 0.5 and 1.5 per mil, indicating the slow-down of deep water circulation and enhanced riverine input of isotopically light dissolved inorganic carbon from terrestrial sources into the eastern Mediterranean Sea. The decrease in epifaunal d13C signals is particularly expressed in the southern Aegean Sea and Levantine Basin, while it is less pronounced in the northern Aegean Sea. This points to a strong reduction in deep water exchange rates in the southern areas, but the persistence of local deep water formation in the northern Aegean Sea. The d13C values of U. mediterranea records reveal temporal and regional differences in paleoproductivity during the past 12 kyr, with rather eutrophic and mesotrophic conditions in the North Aegean Sea and southeast Levantine Basin, respectively, while the South Aegean Sea is characterized by rather oligotrophic conditions. After S1 formation, increasing d13C values reflect a progressive decrease in surface water productivity in the eastern Mediterranean Sea during the middle and late Holocene. In the northern Aegean Sea, this time interval is marked by repetitive changes in organic matter fluxes documented by significant fluctuations in the d13C signal of U. mediterranea on millennial- to multi-centennial time scales. These fluctuations can be linked to short-term changes in river runoff driven by northern hemisphere climatic variability.

Alkenone variations, total organic carbon and stable oxygen isotope ratios of the western Arabian Sea

We here present records of total organic carbon (TOC) and C37 alkenones, used as indicators for past primary productivity, from the western (WAS) and eastern Arabian Sea (EAS). New data from an open ocean site of the WAS upwelling area are compared with similar records from Ocean Drilling Program (ODP) Site 723 from the continental margin off Oman and MD 900963 from the EAS. These records together with other proxies used to reconstruct upwelling intensity, indicate periods of high productivity in tune with precessional forcing. On the basis of their phase relationship to boreal summer insolation they can be divided into three groups: in the WAS differences between monsoonal proxies (1) and productivity (2) document a combined signal of moderate SW monsoon winds and of strengthened and prolonged NE monsoon winds, whereas in the EAS phasing indicates maximum productivity (3) at times of stronger NE monsoon winds associated with precession-related maxima in ice volume.