The Thermodynamics and Geochemistry of Ca, Sr, Ba, and Ra Sulfates in Some Deep Brines From the Palo Duro Basin, Texas

The work reported here involved application of the ion-interaction approach of Pitzer [1] [2] to model the activities of some major and minor cations and major anions in deep brine systems at elevated temperatures and pressures.The solubilities of anhydrite (CaS04), gypsum (CaSO4·2H2O), celestite (SrS04), barite (BaS04), and radium sulfate (RaSO4) in brines from the Wolfcamp Formation and granite wash facies, Palo Duro Basin, Texas, were modeled using ion-interaction equations. Waters with ionic strengths ranging from 2.89 to 4.76 m, and temperatures and pressures up to 40°C and 130 bars were sampled from five horizons in three wells, at depths between 970 and 1,670 meters. Theoretical solubility products as a function of temperature and pressure were obtained for comparison with ion activity products computed using ion-interaction theory. The effect of temperature on model calculations was found to reside almost entirely in the Debye-Hückel AΦ parameter, which accordingly was corrected for brine temperatures [3].Modeling results indicated that all five brines are saturated with respect to anhydrite and celestite, and three of the five with respect to barite. Saturation may result from hydrologic connection with adjacent overlying evaporite units, or increased Ca, Sr and Ba concentrations caused by their desorption from clays. Radium concentrations, which range from 10-11.3 to 10-12.7 m, are not controlled by RaSO4 solubility or adsorption, but probably by solid solution in other sulfate minerals in these low pH (4.4 – 6.3) high calcium (0.18 – 0.52 m) brines [4] [5].