Iodine chemistry in deep anoxic basins and overlying waters of the Mediterranean Sea

Iodate (IO₃⁻) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I⁻) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I⁻ (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO₄³⁻) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.     

Trace elements in suspended matter from the anoxic hypersaline Tyro and Bannock Basins (eastern Mediterranean)

In the anoxic hypersaline Tyro and Bannock Basins of the eastern Mediterranean, extremely high concentrations of Co (0.015%), Cu (1.35%) and Zn (0.28%) were found in suspended matter collected at the sharp interface between seawater and the anoxic brine. The high particulate Co, Cu and Zn concentrations can be explained by the sharp increase in dissolved sulphide at these interfaces, and the resultant precipitation of metal sulphides. The particulate As, Sb and Mo concentrations also showed a sharp maximum at or close to the interface. However, the contributions of As, Sb and Mo contents in suspended matter to the total concentrations in the water column are small. Scanning electron microscopy-energy-dispersive X-ray analysis (SEM-EDAX) of suspended particulate matter from the Tyro Basin revealed spherical particles strongly enriched in Fe, Cu and Zn at the seawater-brine interface.     

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

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 (CaSO₄-2H₂O) and supersaturated to saturated with respect to dolomite (CaMg(CO₃)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 Mn²⁺ 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 (BaSO₄).The ⁸⁷Sr/⁸⁶Sr and δ³⁴S 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.