Search

The Neogene Lake Pannon was the largest lake that ever existed in Europe. It attained its greatest extent during the Tortonian Thermal Maximum. For the first time, results from a detailed lake record documenting about 85 kyr of Late Miocene time in a continuously recovered, 60-m-long, clay-rich core of Lake Pannon are reported. This record includes the transition from the lake's maximum transgression into its highstand at around 10.4 Ma. The environmental development of Lake Pannon during its maximum extent is interpreted based on integrated paleontological, sedimentological, mineralogical and geochemical data. The maximum extent coincided with stable sedimentation of clay, little influx from the hinterland, low surface productivity and severe bottom-water anoxia. The clay mineralogy of the lower part of the core points to prevailing chemical weathering based on the illite/smectite ratios. Distinct Fe, Mn and Ba enrichments are interpreted to have formed close to sulfate-methane transition zones during the maximum flooding. The highstand phase was marked by rapid environmental shifts with frequent phases of well‑oxygenated bottom waters. These phases are reflected by rich benthic communities including stenohaline tunicates. The increased input of detritic kaolinite suggests a shift towards physical weathering and higher precipitation coinciding with a shift in the provenance of clay minerals. Increasing amounts of nutrients stimulated surface water productivity and nannoplankton blooms. Despite the offshore position of the core at ∼8 km from the mountainous ranges of the Alps, strong fluvial input is reflected from 32.5 to 30.3 m by coarser sediment and the occurrence of terrestrial and freshwater molluscs. The Rhenodanubian Flysch Unit was the main source of the siliciclastics of the core and was drained by the Paleo-Wien river. Drainage from the Calcareous Alps was limited to an exceptionally strong fluvial event and related deposits, which documents the presence of a second river in the southwest, which might represent the Paleo-Liesing. The dominance of smectite throughout the core suggests a temperate climate with distinct seasonality during the Tortonian Thermal Maximum. In view of the autochthonous ascidian sclerites in three samples, and assuming generally similar ecological requirements for both Pannonian and modern tunicates, we conclude a polyhaline salinity for Lake Pannon around 10.4 Ma.

International audience; Marine sediments at ocean margins vent substantial amounts of methane. Microbial oxidation of the methane released can trigger the precipitation of carbonate within sediments and support a broad diversity of seafloor ecosystems. The factors controlling microbial activity and carbonate precipitation associated with the seepage of submarine fluid over geological time remain poorly constrained. Here, we characterize the petrology and geochemistry of rocks sampled from metre-size build-ups of methane-derived carbonate chimneys located at the Amon mud volcano on the Nile deep-sea fan. We find that these carbonates comprise porous structures composed of aggregated spherules of aragonite, and closely resemble microbial carbonate reefs forming at present in the anoxic bottom waters of the Black Sea. Using U-series dating, we show that the Amon carbonate build-ups formed between 12 and 7 thousand years ago, contemporaneous with the deposition of organic-rich sediments in the eastern Mediterranean, the so-called sapropel layer S1. We propose that the onset of deep-water suboxic or anoxic conditions associated with sapropel formation resulted in the development of intense anaerobic microbial activity at the sea floor, and thus the formation of carbonate chimneys.

X-ray fluorescence (XRF) core-scanning is a convenient non-destructive tool to rapidly assess elemental variations in unprocessed sediments. However, substantial analytical deviations may occur in such data due to physical sedimentary properties. The consequences of these artifacts on element intensities are important for paleoclimatic studies, but as yet have not been adequately studied for high resolution (≤ 1-cm interval) records. We have done a high resolution comparison between results from XRF scanning and from two more conventional methods: XRF with beads and inductively coupled plasma optical emission spectrometry (ICP-OES), both on discrete samples. Our XRF scan data concord reasonably well with those from the conventional methods for most elements. In several discrete intervals large deviations occur that could have been attributed to major paleoceanographic events. However, these deviations appear to be mainly related to water content and distribution. We show that the variability in the water film thickness underneath the plastic foil is highly variable, causing significant apparent variability in all elements from Al to Fe. The unverified use of these elements in ratios can thus lead to deviations in the paleoenvironmental interpretation. Erroneous element (ratio) variability can, however, be recognized and corrected using conventional analytical data of a few discrete samples. The antipathetic behavior of Ca to K or Ti, and their similar behavior to water absorption, leaves their ratios relatively unaffected at variable water film thicknesses. Hence, Ca/K and Ca/Ti ratios are recommended for a preliminary down-core overview of sedimentary variability and for stratigraphic correlations between unprocessed marine cores.

We investigated the top 30-cm sediment prokaryotic community structure in 5-cm spatial resolution, at an active site of the Amsterdam mud volcano, East Mediterranean Sea, based on the 16S rRNA gene diversity. A total of 339 and 526 sequences were retrieved, corresponding to 25 and 213 unique (≥98% similarity) phylotypes of Archaea and Bacteria, respectively, in all depths. The Shannon-Wiener diversity index H was higher for Bacteria (1.92-4.03) than for Archaea (0.99-1.91) and varied differently between the two groups. Archaea were dominated by anaerobic methanotrophs ANME-1, -2 and -3 groups and were related to phylotypes involved in anaerobic oxidation of methane from similar habitats. The much more complex Bacteria community consisted of 20 phylogenetic groups at the phylum/candidate division level. Proteobacteria, in particular δ-Proteobacteria, was the dominant group. In most sediment layers, the dominant phylotypes of both the Archaea and Bacteria communities were found in neighbouring layers, suggesting some overlap in species richness. The similarity of certain prokaryotic communities was also depicted by using four different similarity indices. The direct comparison of the retrieved phylotypes with those from the Kazan mud volcano of the same field revealed that 40.0% of the Archaea and 16.9% of the Bacteria phylotypes are common between the two systems. The majority of these phylotypes are closely related to phylotypes originating from other mud volcanoes, implying a degree of endemicity in these systems.

For the high-resolution study of trace metal profiles in laminated anoxic sediments, a specially adapted method of resin embedding has been developed. Fluid displacement is the preferred means of sediment dehydration, offering optimum structural preservation and facilitating desalination. Exchanges of deionized water, acetone, and low-viscosity resin are performed in an oxygen-deficient atmosphere to maintain anoxia in the sediments. Analysis of the rinsing fluids indicates both efficient removal of brine salts and minimal dissolution of redox-sensitive trace metals. This contrasts with oxic fluid displacement experiments, in which several metals appear to be removed from the solid phase during desalination. Laser Ablation-Inductively Coupled Plasma- Mass Spectrometry (LA-ICP-MS) scanning of the embedded blocks shows that the adapted preparation viably preserves both the redox-sensitive chemistry and physical structure of the sediment.

The carbon (C) and phosphorus (P) geochemistry of sapropels from four sites in the eastern Mediterranean Sea was determined to obtain more insight into the role of differences in sediment accumulation rates and bottom water anoxia on P regeneration and burial in sediments. Sediment Corg/Porg (with ORG=organic) ratios above Redfield indicate enhanced regeneration of P relative to C from organic matter during formation of the most recent sapropel S1 and a Pliocene sapropel (ODP-site 969E; i-282c). Release of P from Fe-oxides was relatively unimportant. Increased burial of Ca-P (authigenic carbonate fluorapatite and/or biogenic hydroxyapatite) occurred but was of minor importance compared to the enhanced P release from organic matter. For sapropel S1, Corg/Porg and Corg/Preac, (with REAC=reactive, defined as the sum of organic, Fe-bound, authigenic and biogenic Ca-P) ratios decreased with increasing sedimentation rate and oxygen exposure and decreasing water depth. Whether the water column in the deep basin was dysoxic/semi-euxinic (S1) or euxinic (Pliocene) does not appear to affect the estimated burial efficiencies of Porg and Preac. Enhanced Corg burial under the euxinic water column explains the much higher Corg/Porg and Corg/Preac ratios in the Pliocene sapropel (on average ~2860 and ~760, respectively) compared to sapropel S1 (on average ~530 and ~160, respectively)

Studies of past glacial cycles yield critical information about climate and sea-level (ice-volume) variability, including the sensitivity of climate to radiative change, and impacts of crustal rebound on sea-level reconstructions for past interglacials. Here we identify significant differences between the last and penultimate glacial maxima (LGM and PGM) in terms of global volume and distribution of land ice, despite similar temperatures and radiative forcing. Our analysis challenges conventional views of relationships between global ice volume, sea level, seawater oxygen isotope values, and deep-sea temperature, and supports the potential presence of large floating Arctic ice shelves during the PGM. The existence of different glacial ‘modes’ calls for focussed research on the complex processes behind ice-age development. We present a glacioisostatic assessment to demonstrate how a different PGM ice-sheet configuration might affect sea-level estimates for the last interglacial. Results suggest that this may alter existing last interglacial sea-level estimates, which often use an LGM-like ice configuration, by several metres (likely upward).

Quantitative analyses on calcareous nannofossil assemblages on high temporal resolution (600-800 years) have been carried out from Core KC01B in the Ionian Sea (Eastern Mediterranean) throughout Marine Isotope Stage (MIS) 13-9, between 500 and 300 ka. This is an interval of considerable climate changes, known as the Mid-Brunhes event, which includes MIS 11, considered as a possible analogue for future interglacial conditions. In the Mediterranean core, the interval is characterized by the dominance of Gephyrocapsa spp., as also known from ocean records. Calcareous nannofossil abundance fluctuations have been interpreted in terms of modification of sea surface primary productivity/water stratification and temperature. Specifically, the increase in abundance of Gephyrocapsa caribbeanica and small Gephyrocapsa coupled with decreases of Florisphaera profunda, Syracosphaera spp. and Rhabdosphaera spp. suggests enhanced primary productivity/mixed surface waters during interglacial stages and at the Terminations, which can be interpreted in terms of interaction between climate changes and mesoscale oceanographic circulation. On the other hand, distributions of Calciosolenia spp., Oolithotus spp. and Umbilicosphaera sibogae, which are in phase with delta O-18 curve showing higher abundances at the lighter values of the marine isotope record, are considered as warm-water indicators. Biotic proxies point to peculiar climate dynamics through the MIS 12-11 transition (i.e. Termination V). High productive, cool, low salinity and turbid surface waters characterize the early MIS 11(421-408 ka) and likely reflect enhanced continental humidity/monsoon activity over North Africa and increased runoff into the basin. A late surface water warming with respect to Termination V is established at about 403 ka, during a period of low insolation forcing, almost coeval with the deposition of sapropel S11. A climate optimum, lasting about 15 ky (403-389 ka), is then recorded during a period of low insolation forcing centred at 398 ka. The later part of MIS 11 is characterized by climate deterioration at about 389 ka. Comparison with results from subtropical to polar Atlantic records suggests a remarkable relation between Mediterranean and Atlantic climate regimes.

To extend the knowledge of anaerobic ammonium oxidation (anammox) habitats, bacterial communities were examined in two hypersaline sulphidic basins in Eastern Mediterranean Sea. The 2 m thick seawater-brine haloclines of the deep anoxic hypersaline basins Bannock and L'Atalante were sampled in intervals of 10 cm with increasing salinity. N-15 isotope pairing incubation experiments showed the production of N-29(2) and N-30(2) gases in the chemoclines, ranging from 6.0 to 9.2 % salinity of the L'Atalante basin. Potential anammox rates ranged from 2.52 to 49.65 nmol N-2 L-1 day(-1) while denitrification was a major N-2 production pathway, accounting for more than 85.5 % of total N-2 production. Anammox-related 16S rRNA genes were detected along the L'Atalante and Bannock haloclines up to 24 % salinity, and the amplification of the hydrazine synthase genes (hzsA) further confirmed the presence of anammox bacteria in Bannock. Fluorescence in situ hybridisation and sequence analysis of 16S rRNA genes identified representatives of the marine anammox genus 'Candidatus Scalindua' and putatively new operational taxonomic units closely affiliated to sequences retrieved in marine environments that have documented anammox activity. 'Scalindua brodae' like sequences constituted up to 84.4 % of the sequences retrieved from Bannock. The anammox community in L'Atalante was different than in Bannock and was stratified according to salinity increase. This study putatively extends anammox bacterial habitats to extremely saline sulphidic ecosystems.

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (View the MathML sourceSO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate–methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, ‘relict’ barite fronts would only be preserved for a few thousands of years, if at all.

phylotypes, which were previously only detected in anoxic Black Sea sediments. In the same section of the core, the most abundant haptophyte sequence showed highest similarity with uncultivated haptophytes that were previously shown to grow mixotrophically as predators of picocyanobacteria, an adaptation that promotes growth in oligotrophic marine waters. Sequences with highest similarities to clones found in marine surface waters predominated in the S1 after ∼8 14 C kyr B.P. We discuss whether the shifts in haptophyte and dinoflagellate populations inferred from the preserved DNA reflect known environmental changes that occurred during the formation of sapropel S1.

[1] High-resolution laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) scanning of laminated sediments from the Urania basin is used to investigate short-time-scale variability in export productivity and redox conditions during the formation of eastern Mediterranean sapropel S1. Sedimentary enrichments of molybdenum (Mo), vanadium (V), and uranium (U) reflect deep-water redox conditions, most likely those near to the seawater-brine interface, while enrichment of Ba is related to biogenic barite and hence to export productivity. The enrichments of all four elements show strong variability on multidecadal to multicentennial time scales throughout S1. A partial decoupling of export productivity from redox conditions at the height of sapropel formation suggests that hydrographic changes, i.e., a variable ventilation rate of the eastern Mediterranean, played an important role in determining deep-water redox conditions. A pronounced switch is observed in the enrichments of redox-sensitive trace metals, from dominantly 300–600 year variability during early S1 to dominantly 100–300 year variability during late S1, indicating a change in the mean frequency of variability in the ventilation rate. The presence of a similar shift in the frequency of tropical and extratropical climate records at this time suggests that ventilation of the eastern Mediterranean was coupled to global climate variability.

Lithium concentration and isotope data (δ7Li) are reported for pore fluids from 18 cold seep locations together with reference fluids from shallow marine environments, a sediment-hosted hydrothermal system and two Mediterranean brine basins. The new reference data and literature data of hydrothermal fluids and pore fluids from the Ocean Drilling Program follow an empirical relationship between Li concentration and δ7Li (δ7Li = −6.0(±0.3) · ln[Li] + 51(±1.2)) reflecting Li release from sediment or rocks and/or uptake of Li during mineral authigenesis. Cold seep fluids display δ7Li values between +7.5‰ and +45.7‰, mostly in agreement with this general relationship. Ubiquitous diagenetic signals of clay dehydration in all cold seep fluids indicate that authigenic smectite–illite is the major sink for light pore water Li in deeply buried continental margin sediments. Deviations from the general relationship are attributed to the varying provenance and composition of sediments or to transport-related fractionation trends. Pore fluids on passive margins receive disproportionally high amounts of Li from intensely weathered and transported terrigenous matter. By contrast, on convergent margins and in other settings with strong volcanogenic input, Li concentrations in pore water are lower because of intense Li uptake by alteration minerals and, most notably, adsorption of Li onto smectite. The latter process is not accompanied by isotope fractionation, as revealed from a separate study on shallow sediments. A numerical transport-reaction model was applied to simulate Li isotope fractionation during upwelling of pore fluids. It is demonstrated that slow pore water advection (order of mm a−1) suffices to convey much of the deep-seated diagenetic Li signal into shallow sediments. If carefully applied, Li isotope systematics may, thus, provide a valuable record of fluid/mineral interaction that has been inherited several hundreds or thousands of meters below the actual seafloor fluid escape structure.

High-resolution laser ablation–inductively coupled plasma–mass spectroscopy scanning of resin-embedded laminated sediments is used to detail variability in the composition and magnitude of recent eolian dust deposition in the Eastern Mediterranean. The composition of dust accumulating in the anoxic Atalante basin varies in response to the strength of the summer blocking mode of Mediterranean climate. Dust sources located upwind on the westerly airflow are favored during phases of weaker blocking (hence stronger summer westerlies). This mode is in turn correlated to the pronounced multidecadal oscillation in Mediterranean sea-surface temperature (related to the Atlantic Multidecadal Oscillation), suggesting that coupled ocean-atmosphere dynamics control the large-scale transport of dust in the region. Variable precipitation in dust source regions may also exert an influence on the relative flux of dust from each source, and hence the net composition of dust deposited in the basin. Persistent oscillations in the composition of deeper sediments indicate that the basin offers a high-potential archive for reconstruction of climate-controlled variability in dust transport prior to the instrumental era.

The Eastern Mediterranean hosts a variety of active cold seep systems, such as gas chimneys, mud volcanoes and pockmarks, in water depths of 500 to 3200 m. As part of the NAUTINIL expedition in 2003, the sediments of cold seeps on the Nile Deep Sea Fan (NDSF) were sampled for the first time for biogeochemical and microbiological analyses. Here we compare rates of the anaerobic oxidation of methane (AOM) and sulfate reduction (SR) as well as the microbial community structure of a variety of cold seep systems including mud volcanoes, pockmarks and brine seeps. Our results revealed strong differences in microbial activity among the different seep systems of the Eastern, Central and Western provinces of the NDSF, as well as the Olimpi field (Central Mediterranean Ridge). Integrated over a sediment depth of 10 cm below the seafloor, SR rates ranged from 0.1–66 mmol m− 2 d− 1 and AOM rates from 0.1–3.6 mmol m− 2 d− 1. SR was often considerably higher than methane oxidation, indicating that electron donors other than methane were utilized. In general, the lowest rates were associated with pockmarks and carbonate pavements, and highest rates with bacterial mats above the gassy sediments of mud volcano centers. 16S rRNA gene analysis and fluorescence in situ hybridization (FISH), revealed the presence of all known groups of marine methane oxidizing Archaea (i.e. ANME-1, -2, -3) and also of methane oxidizing Bacteria (i.e. Methylobacter sp. and relatives) in some seep sediments. Presumably syntrophic sulfate-reducing bacterial partners of ANMEs were also detected in association with the ANMEs. Several ANMEs formed consortia with unknown bacterial partners. The microbial community structure reflected the presence of typical seep microorganisms at all sites investigated, but differed to varying extents between the different types of seeps. Despite the high availability of methane and sulfate, methanotrophic microbial activity and biomass were lower at the seeps of the Eastern Mediterranean compared to those of other continental margins for unknown reasons.

Con el objetivo de evaluar la relación entre la preservación de escamas de peces y las variaciones en las condiciones redox en sedimentos del margen continental de Chile, este trabajo presenta recuentos de escamas de peces y concentraciones normalizadas de elementos redox sensibles (Mo/Al, S/Al, Fe/Al) en ocho testigos de sedimento recolectados en la zona de minimo oxígeno frente a Chile (Iquique: 20°15' S, bahía de Mejillones: 23° S y Concepción: 36° S). En el norte de Chile (Iquique y Mejillones) predominan las escamas de anchoveta (Engraulis ringens) y de peces de la familia Myctophidae (media = 90 y 120 escamas 1.000 cm-3, respectivamente) mientras que en Chile centro-sur (Concepción) son más abundantes las escamas de jurel (Trachurus murphy; media = 140 escamas 1.000 cm-3). La abundancia de escamas de merluza común (Merluccius gayi gayi) y de sardina (Sardinops sagax) es aproximadamente un orden de magnitud más baja que la de anchoveta o jurel. En general, los valores más altos y los rangos más amplios de variación en las razones Mo/Al, S/Al y Fe/Al se encuentran en Mejillones (Mo/Al ~0,8-12 mg g-1, S/Al 0,2-4,6 g g-1, Fe/Al 0,3-0,7 g g-1) seguidos por Iquique (Mo/Al -0,2-1,8; S/Al 0,2-0,7, Fe/Al 0,5-0,8), mientras que Concepción revela valores más bajos y poco variables (Mo/Al ~0,07, S/Al ~0,15 y Fe/Al ~0,5). La razón Mo/Al, utilizada como indicador de paleo-oxigenación, permite inferir condiciones reductoras relativamente más intensas en los sedimentos de la Bahía de Mejillones e Iquique que en Concepción. En las tres localidades de muestreo se evidencia una asociación estadísticamente significativa entre la abundancia de escamas de anchoveta y el logaritmo de la razón Mo/Al (r²= 0,46; P < 0,0001), apuntando a una dependencia entre estas variables. En especial, para razones Mo/Al < 1 mg g-1, pequeños cambios en las condiciones redox pueden afectar considerablemente la preservación de escamas en el sedimento, mientras que esta dependencia tiende a minimizarse para razones Mo/Al > 1 mg g-1.

Organic-rich sedimentary units called sapropels have formed repeatedly in the eastern Mediterranean Sea, in response to variations of solar radiation. Sapropel formation is due to a change either in the flux of organic matter to the sea floor from productivity changes or in preservation by bottom-water oxygen levels. However, the relative importance of surface-ocean productivity versus deep-water preservation for the formation of these organic-rich shale beds is still being debated, and conflicting interpretations are often invoked. Here we analyse at high resolution the differences in the composition of the most recent sapropel, S1, in a suite of cores covering the entire eastern Mediterranean basin. We demonstrate that during the 4,000 years of sapropel formation, surface-water salinity was reduced and the deep eastern Mediterranean Sea, below 1,800 m depth, was devoid of oxygen. This resulted in the preferential basin-wide preservation of sapropel S1 with different characteristics above and below 1,800 m depth as a result of different redox conditions. We conclude that climate-induced stratification of the ocean may therefore contribute to enhanced preservation of organic matter in sapropels and potentially also in black shales. © 2008 Macmillan Publishers Limited.

[1] XRF sediment core scanning technology is increasingly used to quantify sediment composition. The overall good correlation between biophilic halogen bromine (Br) and sedimentary total organic carbon (TOC) potentially allows the fast estimation of down core TOC profiles by XRF scanning. In order to test this approach we present data from the Arabian Sea and a Mediterranean brine basin, comparing XRF core scanning Br data with discrete sample TOC analyses. Overall, Br counts and TOC show a clear correlation, except when stable carbon isotope and C/N data indicate intervals characterized by enhanced input of terrestrial organic matter. Hence, solid phase Br is exclusively associated with marine organic matter (MOC) and can be used as a direct estimate of this parameter after a calibration is established. High pore water Br in the brine core steepens the Br/TOC correlation but after salt correction shows a nearly identical gradient to that of the Arabian Sea core.

In this study we determined the composition and biogeochemistry of novel, brightly colored, white and orange microbial mats at the surface of a brine seep at the outer rim of the Chefren mud volcano. These mats were interspersed with one another, but their underlying sediment biogeochemistries differed considerably. Microscopy revealed that the white mats were granules composed of elemental S filaments, similar to those produced by the sulfide-oxidizing epsilonproteobacterium “ Candidatus Arcobacter sulfidicus.” Fluorescence in situ hybridization indicated that microorganisms targeted by a “ Ca . Arcobacter sulfidicus”-specific oligonucleotide probe constituted up to 24% of the total the cells within these mats. Several 16S rRNA gene sequences from organisms closely related to “ Ca . Arcobacter sulfidicus” were identified. In contrast, the orange mat consisted mostly of bright orange flakes composed of empty Fe(III) (hydr)oxide-coated microbial sheaths, similar to those produced by the neutrophilic Fe(II)-oxidizing betaproteobacterium Leptothrix ochracea . None of the 16S rRNA gene sequences obtained from these samples were closely related to sequences of known neutrophilic aerobic Fe(II)-oxidizing bacteria. The sediments below both types of mats showed relatively high sulfate reduction rates (300 nmol·cm −3 ·day −1 ) partially fueled by the anaerobic oxidation of methane (10 to 20 nmol·cm −3 ·day −1 ). Free sulfide produced below the white mat was depleted by sulfide oxidation within the mat itself. Below the orange mat free Fe(II) reached the surface layer and was depleted in part by microbial Fe(II) oxidation. Both mats and the sediments underneath them hosted very diverse microbial communities and contained mineral precipitates, most likely due to differences in fluid flow patterns.

Four mud volcanoes of several kilometres diameter named Amon, Osiris, Isis, and North Alex and located above gas chimneys on the Central Nile Deep Sea Fan, were investigated for the first time with the submersible Nautile. One of the objectives was to characterize the seafloor morphology and the seepage activity across the mud volcanoes. The seepage activity was dominated by emissions of methane and heavier hydrocarbons associated with a major thermal contribution. The most active parts of the mud volcanoes were highly gas-saturated (methane concentrations in the water and in the sediments, respectively, of several hundreds of nmol/L and several mmol/L of wet sediment) and associated with significantly high thermal gradients (at 10 m below the seafloor, the recorded temperatures reached more than 40 °C). Patches of highly reduced blackish sediments, mats of sulphide-oxidizing bacteria, and precipitates of authigenic carbonate were detected, indicative of anaerobic methane consumption. The chemosynthetic fauna was, however, not very abundant, inhibited most likely by the high and vigorous fluxes, and was associated mainly with carbonate-crust-covered seafloor encountered on the southwestern flank of Amon. Mud expulsions are not very common at present and were found limited to the most active emission centres of two mud volcanoes, where slow extrusion of mud occurs. Each of the mud volcanoes is fed principally by a main narrow channel located below the most elevated areas, most commonly in the centres of the structures. The distribution, shape, and seafloor morphology of the mud volcanoes and associated seeps over the Central Nile Deep Sea Fan are clearly tectonically controlled.

[1] The residual dark unit of the most recent eastern Mediterranean sapropel (S1) is usually overlain by sediments with enhanced concentrations of MnOx in two separated layers. The variability and magnitude of the Mn enrichment at different locations and water depths indicate that Mn must have been added preferentially to sediments at intermediate (1–2 km) water depths. We propose a two-stage mechanism for the Mn enrichment that involves decreasing oxygenation with increasing water depth. This mechanism involves the loss of reduced Mn2+ from the deepest sediments (>2 km water depth) into overlying anoxic waters and a variable gain of MnOx in sediments in contact with oxygenated waters at shallower depth. In the S1 unit that receives the extra MnOx input, an upper higher Mn-enriched zone (>3 wt %) is maintained continuously at the top of the accumulating S1 unit because the pore waters are anoxic at shallow sediment depth while bottom waters are oxic to some degree. In a reactive-transport model, the Mn enrichment in the upper zone could not be supported by normal sediment diagenesis. Thus the MnOx in the upper Mn horizon must have formed mainly in the water column. The MnOx in the upper Mn-enriched zone adsorbed Mo and Li from seawater in a similar manner as other Mn-enriched oxic sediments, nodules, and crusts, with a Mn:Mo ratio of ∼600:1, a Mn:Li ratio of ∼750:1, and a δ98/95MoMOMO of −2.5 ‰.

The Holocene-late Pleistocene distribution of holococcoliths, is quantified by light microscopy from cores from the Western Mediterranean, the Aegean Sea and eight eastern Mediterranean cores recovering sapropel S1. The diversity of fossil holococcoliths is much lower than is seen in the plankton, indicating selective preservation. However the holococcolith phases of Syracosphaera pulchra and Helicosphaera carteri are abundantly preserved allowing a comparison of fossil records of heterococcolith and holococcolith phases of these species. In shallow cores a primary palaeocological signal appears to be preserved, suggesting that under suitable circumstances it is possible to use holococcoliths in palaeoceanography. The common occurrence of holococcoliths in the sapropels from these cores suggests low surface-water productivity, supporting previous inferences that productivity enhancement during sapropel deposition was confined to the deep-chlorophyll maximum. In deeper cores there is dramatic decrease in abundance of S. pulchra holococcoliths within sapropel sediments. From comparison of shallow and deep cores and from Emiliania huxleyi preservation data we conclude that this is a preservation signal. Evidently the calyptroliths produced by S. pulchra have a lower preservation potential than the syracoliths produced by H. carteri, we interpret this as a product of their more open structure. © 2005 Elsevier B.V. All rights reserved.

Clarification of the factors involved in the formation of unusual ancient organic carbon- rich deposits (like eastern Mediterranean sapropels) is central in understanding oceanic carbon cycling. The role of oxygenation remains a subject of controversy primarily due to two major uncertainties: (1) it is unknown if ancient organic-rich deposits reflect an accumulation of refractory organic matter (OM) or oxygenation-related aberrant sediment OM recycling, and (2) although marine OM degradation may be slower under anoxic conditions, its ultimate impact on organic carbon (Corg) preservation over geological time remains unclear. Here we provide direct experimental evidence that the Corg in eastern Mediterranean S1 sapropels (deposited .5 ka) is still highly reactive and that a shutdown in labile organic matter degradation under anoxic conditions played a key role in the formation of these deposits.

Deep hypersaline anoxic basins in the Mediterranean Sea are a legacy of dissolution of ancient subterranean salt deposits from the Miocene period. Our study revealed that these hypersaline basins are not biogeochemical dead ends, but support in situ sulfate reduction, methanogenesis, and heterotrophic activity. A wide diversity of prokaryotes was observed, including a new, abundant, deeply branching order within the Euryarchaeota . Furthermore, we demonstrated the presence of a unique, metabolically active microbial community in the Discovery basin, which is one of the most extreme terrestrial saline environments known, as it is almost saturated with MgCl 2 (5 M).

Phosphorus regeneration and burial fluxes during and after formation of the most recent sapropel Sl were determined for two deep-basin, low-sedimentation sites in the eastern Mediterranean Sea. Organic C/P ratios and burial fluxes indicate enhanced regeneration of P relative to C during deposition of sapropel S1. This is largely due to the enhanced release of P from organic matter during sulfate reduction. Release of P from Fe-bound P also increased, but this was only a relatively minor source of dissolved P. Pore-water HPO42- concentrations remained too low for carbonate fluorapatite formation. An increased burial of biogenic Ca-P (i.e., fish debris) was observed for one site. Estimated benthic fluxes of P during sapropel formation were elevated relative to the present day (similar to900 to 2800 vs. similar to70 to 120 mumol m(-2) yr(-1)). The present-day sedimentary P cycle in the deep-basin sediments is characterized by two major zones of reaction: (1) the zone near the sediment-water interface where substantial release of HPO42- from organic matter takes place, and (2) the oxidation front at the top of the S1 where upward-diffusing HPO42- from below the sapropel is sorbed to Fe-oxides. The efficiency of aerobic organisms in retaining P is reflected in the low organic C/P ratios in the oxidized part of the sapropel. Burial efficiencies for reactive P were significantly lower during Sl times compared with the present day (similar to7 to 15% vs. 64 to 77%), Budget calculations for the eastern Mediterranean Sea demonstrate that the weakening of the antiestuarine circulation and the enhanced regeneration of P both contributed to a significant increase in deep-water HPO42- concentrations during sapropel S1 times. Provided that sufficient vertical mixing occurred, enhanced regeneration of P at the seafloor may have played a key role in maintaining increased productivity during sapropel S1 formation.

Sapropels—organic-matter rich layers—are common in Neogene sediments of the eastern Mediterranean Sea. The formation of these layers has been attributed to climate-related increases in organic-matter production1,2,3 and increased organic-matter preservation due to oxygen depletion in more stagnant bottom waters2,3. Here we report that eastern Mediterranean Pliocene sapropels4 contain molecular fossils of a compound (isorenieratene) known to be synthesized by photosynthetic green sulphur bacteria, suggesting that sulphidic (euxinic)—and therefore anoxic—conditions prevailed in the photic zone of the water column. These sapropels also have a high trace-metal content, which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column. The abundance and sulphur-isotope composition of pyrite are consistent with iron sulphide formation in the water column. We conclude that basin-wide water-column euxinia occurred over substantial periods during Pliocene sapropel formation in the eastern Mediterranean Sea, and that the ultimate degradation of the increased organic-matter production was strongly influential in generating and sustaining the euxinic conditions.

Two cores recovered from different locations in the eastern Mediterranean contain intercalations of organic-rich sapropels in organic-poor hemipelagic sediments. In both cores enrichments of Mn and Fe were found in the oxidised section of the sediment, above the sapropel S1. The sediments followed a diagenetic cycle, which began after the sapropel formation finished (about 7000 years ago). First, during a non-steady-state diagenetic phase, metal-rich layers were formed at a downward moving oxidation front. The front decelerated at the top of the sapropel as a consequence of increasing amounts of Corg and sulphides that had to be oxidised. During the second part of this non-steady-state phase, the oxidation front starts moving upwards with respect to the sapropel. Manganese is remobilised in preference to iron due to thermodynamics, reinforced by kinetics. When the upward movement of the oxidation front becomes equal to the sedimentation rate, steady-state is established with respect to the new organic-poor sedimentary circumstances. At location 31G1, the system is at or close to steady-state. At location 9G1, however, this steady-state phase has never been reached. Between 1900 and 1350 years BP, the organic carbon accumulation rate probably increased suddenly, inducing a retreat of the oxidation front and the non-steady-state formation of double peaks.

Distinctly coloured trace metal enriched fronts with a six-fold Cu-enrichement occur in the interbedded pelagic-turbiditic sediments from the Madeira Abyssal Plain. To decipher their mode of formation, two sequential extraction techniques, an acid-gradient and a “Tessier-type” scheme, were applied. Two different front types could be distinguished: Type-1 fronts are mostly black and enriched in Co, Zn, Ni and Cu, and associated with the oxidation fronts that developed after deposition of turbidites. Type-2 fronts are purple, extremely enriched in Cu, and associated with sulphur. These fronts are sometimes found in relation with a relict oxidation front, but often show no clear relation with lithology. Two different modes of formation are postulated. (1) The transition-metal enrichment in the type-1 fronts is typical for a manganese-oxide association often found in marine sediments. After the dissolution of manganese-oxide during sub-oxic diagenesis, the transition metals were liberated and subsequently relocated and precipitated in response to a redox-gradient. (2) The CuS association in type-2 fronts is also formed during sub-oxic diagenesis. The main process leading to the formation of this CuS enrichment is the mobilization of inherited CuS compounds from organic-rich turbidites. The accumulation of these compounds is possibly related to redox changes at relict oxidation fronts and to gradual, probablly slowly evolving, redox changes that occur at present.

Authigenic dolomite layers occur in the organic matter-rich sediments of Kau Bay, Indonesia. Dolomite formation is related to the anaerobic decomposition of organic matter which causes depletion of pore-water sulfate and increase in interstitial water alkalinity. X-ray diffractograms of Kau Bay dolomites show sharply defined peaks, including the superstructure reflections. Carbon isotopes indicate that a significant portion of the carbon is derived from the degradation of organic matter. The pore waters are highly supersaturated with dolomite, but at greater depths, pore waters are undersaturated or are near saturation with calcite and aragonite. Dolomite seems to have formed by direct precipitation from solution. The formation of dolomite is believed to be initiated by the high alkalinity levels found in the zone of anoxic methane oxidation. The rate of dolomite formation is controlled by the supply of calcium and is on the order of a few centimetres per 1 ka.

THE deposition of large amounts of radiocaesium from nuclear weapons testing and from accidents such as Chernobyl has necessitated study of the fate of these long-lived radioisotopes in the natural environment. Caesium is known to interact strongly with micaceous clay minerals in soils and sediments1–4. Radiocaesium can therefore be removed from the water column in lake systems by settling particles and surface sediments5. This process reduces its mobility and the risk of assimilation by biota. Nevertheless, there are indications that radiocaesium may be mobilized from lacustrine anoxic sediments6. Direct evidence, however, can come only from measurements on pore water from lake sediments, and here we report such measurements. Actual in situsolid/liquid distribution coefficients (Kd values), determined from our data, provide convincing evidence for post-depositional mobilization of particle-bound 137Cs. This is probably caused by ion exchange with NH4+which reaches high concentrations in anoxic pore waters. The pore-water data indicate that radiocaesium is returned to the water column and thus becomes available for uptake by aquatic organisms.

Pyrite within and below sapropels in the eastern Mediterranean is a result of microbial SO42- reduction within the sapropel, and the subsequent reaction of sulfide (HS-) with detrital Fe and Fe2+ diffusing upward from underlying sediments. Below the youngest Mediterranean sapropel, S1, pyrite (as much as 281 mu mol pyritic S/g) is mostly present as euhedral crystals, whereas within the sapropel only framboidal pyrite (as much as 360 mu mol pyritic S/g) has been detected. Framboidal microtextures indicate pyrite formation at the site of HS- production within the sapropel. Euhedral pyrite, below the sapropel, forms when sulfate reduction in the sapropel outcompetes iron liberation and supply, and HS- diffuses out of the sapropel. Sulfur isotope values of pyrite are extremely light in the sapropel (-37.3 parts per thousand to -38.2 parts per thousand) as well as below the sapropel (-45.6 parts per thousand and -49.6 parts per thousand), indicating that HS- has formed in a system with abundant SO42- and in the presence of oxidants. [KEYWORDS: Laboratory synthesis; marine-sediments]