New insights into fluid-rock interaction mechanisms at mud volcanoes: Implications for fluid origin and mud provenance at Bahar and Zenbil (Azerbaijan)

Understanding the fluid-rock interactions occurring in terrestrial mud volcanoes is a premise for elucidating the (bio)geochemical processes involved in the release of aqueous fluids, mud and gases to the Earth's surface and atmosphere. For the first time, fluid and mud ejecta from the mud volcanoes at Bahar and Zenbil, located in eastern Azerbaijan and in the shallow coastal water of the South Caspian, were collected and analyzed for their mineralogical, textural and chemical composition. The expelled aqueous fluids have a Na-Cl-(HCO₃) composition and are generated by the mixing of evaporitic Caspian seawater and ancient, low- to high-salinity, sedimentary pore water at temperatures of 32 ± 3 °C and 42 ± 5 °C for the mud volcanoes at Bahar and Zenbil, consistent with mud chambers to be situated in the Pliocene sediments at 2–3 km depth. These aqueous fluids are strongly enriched in major solutes, like Na, Cl, HCO₃, B, Br, NH₄ and DOC, as well as in some trace elements (As, Ba, Cu, Fe, Li, Sr and Zn), with concentrations up to 220 times that of the current Caspian seawater. This chemical concentration is caused mainly by a combination of (i) strong surface evaporation, ion exchange and adsorption-desorption involving smectite clays, redox-driven reactions and carbonate mineral precipitation at relatively shallow depths (not deeper than 4 km) as well as (ii) thermal breakdown of organic matter and methane production in deeply buried (4 to 7 km depth) organic-rich strata. Biogenic processes are only of minor importance. The mud is sourced from all horizons the mud volcanoes are cross-cutting, partly altered by diagenetic processes. Alteration is comprised of illitization of smectite during burial diagenesis (120 to 150 °C), replacements of feldspar by kaolinite and smectite, weathering of sulfide minerals, Fe-(oxy)hydroxide formation, as well as oxidation of methane and organic matter in the near sub-surface environments at low temperature (<40 °C). Our results indicate that fluid-mud mixtures expelled from mud volcanoes of the South Caspian basin can influence the chemistry of local surface and ground water as well as of (sub-)surface sediments.