Sulphate-related equilibria in the hypersaline brines of the Tyro and Bannock Basins, eastern Mediterranean

Abstract

The Tyro and Bannock Basins, which are depressions in the eastern Mediterranean, contain hypersaline anoxic brines. These brines are of different composition: Tyro brine is primarily an early-stage halite (NaCl) brine, whereas Bannock brine includes the more soluble ions of late-stage evaporite minerals. Accordingly, the Bannock brine contains a much greater sulphate concentration than the Tyro Brine. This difference in sulphate concentration is reflected in the concentrations of ions such as Ca, Sr and Ba, which form sparingly soluble sulphate minerals. Equilibrium calculations using the Pitzer specific ion interaction model indicate that the brines in both basins are saturated with respect to gypsum (CaSO 4-2H 2O) and supersaturated to saturated with respect to dolomite (CaMg(CO 3) 2). The degree of saturation with respect to dolomite is greater in the Bannock Basin than it is in the Tyro Basin. Correspondingly, recent gypsum crystals and dolomite hardgrounds have been found in the Bannock Basin but not in the Tyro Basin. The Tyro brine is homogeneous in composition, whereas the Bannock brine demonstrates a clear two-layer brine structure. At the interface of the upper and the lower brine distinct positive anomalies occur in the total alkalinity and the concentration of phosphate, and negative anomalies occur in the concentrations of Mn 2+ and the rare earth elements (REE). These anomalies and the observed association of gypsum/dolomite in the sediments are all consistent with a recent precipitation of dolomite and gypsum in the Bannock Basin. The brines in both basins are also saturated with respect to barite (BaSO 4). The 87Sr/ 86Sr and δ 34S ratios of the Bannock brines are amazingly consistent but differ dramatically from the values for modern or Messinian-age seawater. The Sr concentration and Sr and S isotope ratios in the gypsum crystals indicate that most of these crystals have resulted from precipitation/recrystallization from the brine and not from seawater. The observed variations between crystals are thought to reflect the recrystallization of (sub-) outcropping Messinian gypsum with a low 87Sr/ 86Sr ratio in the presence of seawater or brine fluids and with different extents of diagenesis.