Messinian Ca–Cl Brines from Mediterranean Basins: Tracing Diagenetic Effects by Ca/Mg Versus Ca/Sr Diagram

In natural resource exploration, Ca–Cl basinal brines are important for understanding the origin and spatial and temporal distribution of hydrocarbons and sedimentary ore deposits. Little attention has been paid to the possible connection between fossil basinal brines and paleo-seawaters and to the implications for reconstructing paleoseawater compositions. Secular variations of Ca/Mg and Ca/Sr ratios in seawater have been documented mainly using fluid inclusions in halite, calcareous fossils and mineral analyses. However, brines and other sedimentary records connected to paleo-seawater or its evaporated residues may be chemically affected by burial diagenesis or the effects of continental waters of meteoric origin, thus complicating interpretations of the analytical results. To investigate these effects on fluids and minerals related to the Messinian salinity crisis of the Mediterranean basin, we re-evaluate published data from: (1) brackish-to-brine waters from onshore (Northern Apennine foredeep; Levantine basin) and offshore (porewaters from the Deep Sea Drilling Project); (2) Messinian parental seawater deduced from calcareous fossils, fluid inclusions and sulfate minerals; (3) meteoric waters dissolving evaporites. The compositional trends related to seawater evaporation, diagenesis and mixing that affect the Ca/Mg and Ca/Sr molar ratios of the basinal brines are effectively discriminated on a binary plot depicting the proper fields for seawater and meteoric derived fluids. Brines showing stronger dolomitization start from Ca/Mg and Ca/Sr molar ratios of Messinian seawater deduced from the published analysis of fluid inclusions and open ocean fossils, that are therefore here validated ex post.