ALBERT

Description: 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.

Description: 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 invoked1, 2, 3, 4, 5, 6, 7. 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.

Description: 10.1016/j.epsl.2005.10.027

Description: The pore water chemistry of mud volcanoes from the Olimpi Mud Volcano Field and the Anaximander Mountains in the eastern Mediterranean Sea have been studied for three major purposes: (1) modes and velocities of fluid transport were derived to assess the role of (upward) advection, and bioirrigation for benthic fluxes. (2) Differences in the fluid chemistry at sites of Milano mud volcano (Olimpi area) were compiled in a map to illustrate the spatial heterogeneity reflecting differences in fluid origin and transport in discrete conduits in near proximity. (3) Formation water temperatures of seeping fluids were calculated from theoretical geothermometers to predict the depth of fluid origin and geochemical reactions in the deeper subsurface. No indications for downward advection as required for convection cells have been found. Instead, measured pore water profiles have been simulated successfully by accounting for upward advection and bioirrigation. Advective flow velocities are found to be generally moderate (3–50 cm y− 1) compared to other cold seep areas. Depth-integrated rates of bioirrigation are 1–2 orders of magnitude higher than advective flow velocities documenting the importance of bioirrigation for flux considerations in surface sediments. Calculated formation water temperatures from the Anaximander Mountains are in the range of 80 to 145 °C suggesting a fluid origin from a depth zone associated with the seismic decollement. It is proposed that at that depth clay mineral dehydration leads to the formation and advection of fluids reduced in salinity relative to sea water. This explains the ubiquitous pore water freshening observed in surface sediments of the Anaximander Mountain area. Multiple fluid sources and formation water temperatures of 55 to 80 °C were derived for expelled fluids of the Olimpi area.

Description: Suboxic sapropel S1 sediments of the eastern Mediterranean carry an untypically light δ98/95Mo signal, being even lighter than oxic Mn-enriched sediments and Mn-crusts/nodules, which were previously thought to carry the lightest Mo isotope values. The evaluation and comparison of oxic S1, diagenetically overprinted oxic S1, and suboxic S1 sediments indicates that this light isotope signal is primarily an oxic signal that has been overprinted by secondary diagenetic processes occurring after sediment burial. Such secondary processes bear the potential of additional Mo isotope fractionation in particular in non-steady state diagenetic environments that involve the discontinuous re-location of the redox boundary.

Description: CaCO3 contents in eastern Mediterranean sapropels are generally lower than in the enclosing marl sediments. In sediments of a transect from ∼ 650 to 2100 m water depth at the Sirte continental slope, the opposite feature was observed. Although the increased Sr/Ca ratios observed in these sediments agree with such feature observed in other eastern Mediterranean S1 sediments, their absolute magnitude is much higher. The enhanced Sr/Ca ratio in these sediments is associated with their aragonite content, which for the Sirte transect reaches levels of up to ∼ 40 wt.%. The aragonite content and Sr/Ca ratios in the S1 sediments of this transect decrease with increasing water depth and decrease with distance to the African coast for all eastern Mediterranean cores. In view of the lack of a coherent relationship with sedimentary reduced sulphur contents and porosity, and considering the major amount of aragonite found specifically in the sediments of the Sirte transect, authigenic precipitation can contribute only a limited fraction at most. SEM observation and electron-microprobe analyses showed that the needles and needle clusters are morphologically aragonite, contain the highest Sr/Ca ratio, and are similar to skeleton fragments of the green alga Halimeda. Consequently, a detrital/biogenic source is the likely mechanism for the major part of the aragonite enrichments found in S1 sediments. Possibly, offshore-directed surface water flows related to wind stress and/or enhanced run-off (consistent with enhanced precipitation during sapropel S1) may have assisted in the transport of near-coastal aragonitic organisms to more coast-remote areas.