Carbon, oxygen and strontium isotopic constraints on fluid sources, temperatures and biogeochemical processes during the formation of seep carbonates - Secchia River site, Northern Apennines

Understanding authigenic seep carbonate formation provides clues for hydrocarbon exploration and insights into contributions to gas budgets of marine environments and the atmosphere. Seep carbonates discovered in the outcropping succession along the Secchia riverbanks (near Modena, Italy) belong to the Argille Azzurre Formation of Early Pleistocene age deposited in an upper shelf environment overlying the Miocene foredeep successions, which include hydrocarbon fields. The fluid migration from the hydrocarbon fields, up to the surface, is presently active on land and started in the marine succession during the Late Miocene. Authigenic globular carbonate concretions and carbonate chimneys are interspersed along the strata throughout the section. A comprehensive geochemical characterisation of the carbonates has been carried out to understand the processes leading to their formation. The carbonate concretions are the record of past hydrocarbon vents linked to the Miocene petroleum system of the Northern Apennines. The samples are composed of > 50% microcrystalline dolomite. The δ13C signatures identify two groups in the samples according to different type of formation processes. Globular concretions have positive values that suggest an influence of CO2 associated to secondary methanogenesis due to microbial degradation of higher hydrocarbons. The analysed chimney, with negative δ13C values, is interpreted as former conduit where carbonate precipitation is promoted by Anaerobic Oxidation of Methane coupled with Sulfate Reduction. The δ18O range, coupled with 87/86Sr signatures, indicate that the contribution of deep connate water from the Miocene reservoirs is up to 23% during the formation of the globular concretions. The connate water occurrence is also documented by higher ambient temperatures. The different isotope signatures in seep carbonates result from the relative contribution of the recognised gas and water components, linked to different plumbing systems and fluid supply from a well-defined hydrocarbon field. The seep carbonate characteristics have enlightened variations in biogeochemical processes, which can be rarely quantified in ancient and present-day marine environments.