Chemical and isotope composition of the oilfield brines from Mishrif Formation (southern Iraq): Diagenesis and geothermometry

This paper focuses on the geochemical composition and isotope geochemistry of brines in the Cenomanian–Turonian carbonate Mishrif reservoir of southern Iraq. Main dissolved constituents, trace elements, δ2H and δ18O, 87Sr/86Sr, mineral saturation indices and thermodynamic calculations were investigated in formation waters from the Mishrif Formation to obtain a better understanding of brine evolution and diagenetic effects over geological time. Previous published δ11B data were also reinterpreted as a geothermometer tool. The results are compared with previous published data for local oilfields and coeval formations in the Arabian Gulf. The Mishrif brine has a marine origin and is diagenetically modified to Ca-excess and Na-deficit. Formation waters are quartz supersaturated and are in equilibrium with chalcedony and calcite-dolomite in the temperatures range of 50–75 °C, which is also confirmed by calcite-water oxygen isotope fractionation and δ11B geothermometer. The potential role of clays in conditioning brine chemistry during diagenetic processes was highlighted by activity diagrams; in particular, their adsorption/exchange effect on sodium could explain the lower temperature obtained by the Na/Li geothermometer (42 ± 6 °C). The δ2H and δ18O values show that oxygen isotope composition of the brines was isotopically more affected by interaction with limestone during diagenesis than seawater evaporation. The main effect is an 18O-enrichment on the brine starting from the SMOW value. Locally, dilution by present-day meteoric water was also detected (Rumaila South), which is shifted towards the local meteoric water line. The strontium isotope ratios range from 0.707713 to 0.707749 and correspond to a marine strontium of late Cenomanian–early Maastrichtian age, except for the Majnoon sample, which shows a more radiogenic value (0.708043). Radiogenic strontium and gypsum and anhydride saturation indices of the Majnoon sample could indicate the contribution of calcium and sulphate from the strontium-rich sulphate minerals of the Cambrian salt domes occurring in the oilfields of southern Iraq. The higher manganese concentration (4 mg/l) and the slightly higher temperature inferred by geothermometers (up to 74 °C) in comparison with present-day could indicate that the Majnoon brine is a hot fluid, probably related to a deeper structure such as the Zagros Foredeep Fault.