Abstract: Chlorine is the most abundant halogen in sedimentary formation waters with concentrations from <100 to >250000 mg/l. Bromine is the second most abundant halogen at <1 mg/l to >6000 mg/l with iodine from <0.1 mg/l to >100 mg/l and fluorine from <0.1 mg/l to 30 mg/l. Chlorine and bromine show a strong systematic covariation suggesting that they are subject to the same controlling mechanisms. Fluorine only shows relatively high concentrations at elevated chlorine and bromine concentrations showing that fluorine, chlorine and bromine are possibly controlled by the same processes. Iodine does not correlate with any of the other halogens indicating that unique processes control iodine.
Key geological parameters that influence chlorine and bromine (and possibly fluorine) concentrations are the presence of salt in a basin, the age of the reservoir unit and the kerogen-type within the main hydrocarbon source rock in a basin. The presence of salt in a basin shows that sea water was evaporated to halite saturation producing connate waters with high concentrations of chlorine and bromine. The presence of salt also leads to high salinity waters through water-salt interaction during burial and diagenesis. Tertiary reservoirs typically have much lower chlorine and bromine concentrations than Mesozoic or Palaeozoic reservoirs. The age of the reservoir unit may simply reflect the different amounts of time available for formation water to interact with salt. The dominance of type II marine kerogen in a basin leads to higher bromine concentrations. This may reflect the dominance of a marine influence in a basin which is more likely to lead to salt deposition than terrestrial depositional environments. Iodine concentrations are independent of all these parameters. Other geological parameters such as depth of burial, temperature, basin forming mechanism and reservoir lithology have no influence upon halogen concentrations.
Key processes that affect halogen concentrations are sea water evaporation and dilution, water—salt interaction and input from organic sources. Chlorine and bromine data lie close to the experimentally-derived sea water evaporation trend showing that sea water evaporation may be an important general control on halogens. Sea water dilution is probably responsible for most low salinity formation water chlorine and bromine concentrations for the same reason. Sea water dilution can occur either by meteoric invasion during burial, or following uplift and erosion, or by diagenetic dehydration reactions. Water can interact with salt in a variety of ways: halite dissolution by congruent processes, halite recrystallization by incongruent processes, sylvite dissolution or recrystallization and halite fluid inclusion rupture. Halite dissolution will lead to high chlorine and relatively low bromine waters because halite contains little bromine. In contrast, halite recrystallization will lead to bromine-enhanced waters because NaBr dissolves preferentially to NaCl. The occurrence of dissolution or recrystallization will depend on the water rock ratio, greater volumes of water will lead to more dissolution and waters with higher Cl/Br ratios. Sylvite is usually rich in bromine so dissolution will lead to bromine-enhanced waters. Primary aqueous inclusions in halite contain high bromine concentrations so that rupture, during deformation or recrystallization, will lead to bromine-enhanced formation water. A combination of these processes are responsible for the very limited range of Cl/Br ratios although congruent halite dissolution must have a limited role due to the absence of waters with high Cl/Br ratios.
Iodine is strongly concentrated in organic materials in the marine environment; oils and organic rich-source rocks have high I/Cl and I/Br ratios relative to sea water or evaporated sea water. All formation waters are enriched in iodine relative to sea water implying that there has been input from organic matter or interaction with oil. However, hydrocarbon source rock type in a basin has no discernible effect upon iodine concentrations.