Origin And Chemical Evolution Of Brines In Sedimentary Basins

Brines (a solution containing more than 100,000 mg/l dissolved solids) in sedimentary basins are genetically related to evaporites in one of three ways: (1) dissolution of evaporite minerals, generally halite; (2) interstitial fluids in evaporites which are expelled from their source rock during compaction; (3) incongruent alteration of hydrous evaporite minerals (carnallite). Most brines of commercial interest originate as interstitial fluids in halite-rich rocks. These fluids are initially rich in magnesium, sulfate, and potassium but evolve in composition to an Na-Ca-Cl brine during their migration to their present host rock. A particularly important reaction in this process is: 2CaCO3 + Mgt+ = CaMg(CO3)2 + Cat (1a) This reaction reduces the magnesium content of the brine and ultimately converts it to a calcium-rich brine. The loss of sulfate occurs by two mechanisms. One of these is by direct precipitation as calcium sulfate (either as gypsum or anhydrite): Ca 2+ + SO4 2- = CaSO4 (2a) Additional sulfate may be lost from the brine by sulfate reduction: S042 + 1.33CH2 + 214- = H2S + 1.33CO2 + 1.33H20 (3a) The loss of carbonate species occurs by precipitation as carbonates: H2O + C02 + Cat = CaCO3 + 2H+ (4a) The net result of reactions 3 and 4 is: Ca 2+ + SO4 2- + 1.33CH2 = H2S + CaCO3 + 0.33H2O + 0.33CO2 (5a) The loss of potassium from brines is caused by the formation of potassium aluminosilicates: 2K+ + Al2Si2O5 (OH)4 + 4SiO2 = 2H + 2KAlSi2O8 + H2O (6a) The hydrogen ions produced by this reaction dissolve carbonates: 2H+ + CaCO3 = Ca 2+ + CO2 + H2O (7a) The net result of reactions 6 and 7 is: 2K+ + CaCO3 + Al2Si205 OH)4 + 4SiO2 = Ca2 + 2KA1Si3O8 + H2O + C02 (8a) A study of brines from central Mississippi has shown that the composition of these brines is related to the interaction of pore fluids from evaporites with minerals in the enclosing sedimentary rocks.