Evidence of methane venting and geochemistry of brines on mud volcanoes of the eastern Mediterranean Sea

As a part of the Dutch–French MEDINAUT diving expedition in 1998, cold seeps and mud volcanoes were studied and sampled in two distinctive tectonic settings in the eastern Mediterranean Sea. The first setting was the Olimpi Mud Volcano field (OMV area), including Napoli, Milano, Maidstone and Moscow mud volcanoes, south of Crete on the Mediterranean ridge. The second setting was the Anaximander Mountains (AM area), southwestern Turkey, where Amsterdam, Kazan and Kula mud volcanoes were explored. Large methane concentrations (45–892 nmol/kg) were measured in the water column not only above mud volcanoes but also in seeps and vents along related fault systems, indicating intense degassing related to fluid circulation in sediments. The tracer results show that there is considerable variability in terms of gas seepage and matter flux between these mud volcanoes. Brine accumulations found as shallow pools on Napoli or associated with deep faults (Nadir Lake) outside mud volcanoes exhibit variable chlorinity, mineral and gas composition. The brines are significantly enriched in δ18O relative to ambient seawater and are consistent with evaporated seawater. In the Nadir Brine Lake, the level of methane is as high as 5.93 mmol/kg, lower than the methane saturation level of 120 mmol/kg theoretically found at the salinity (120), pressure (200 bar), and temperature (13.6°C) conditions of Nadir lake. In contrast, the shallow brine pools on Napoli mud volcano (also OMV area) have methane levels of only 4.45 μmol/kg. In all brines, helium data show a clear radiogenic isotopic ratio (R=0.06×Ra), in excellent agreement with recently published data for the Urania basin. Methane to ethane ratios (>1000) and δ13C(CH4) values (−65.6‰PDB) indicate that the CH4 is microbially produced. Unlike mid-ocean ridges, where abiogenic methane and helium have a common origin in the brines, the large variation in the CH4/He ratio indicates that CH4 and helium sources are unrelated, a fact that adds further support to the biogenic origin of methane. These results show that mud volcanoes in the eastern Mediterranean Sea are important sites of extensive biogenic methane fluxes, which are probably related to widespread occurrences of gas hydrates.