Elemental and isotope geochemistry of Smackover Formation brines in Alabama and Arkansas: Implications for fluid mixing and water-rock interaction

This study investigates the geochemical characteristics of brines within the Upper Jurassic Smackover Formation in Alabama and Arkansas through elemental and isotopic analyses and geochemical modeling to reveal the extent and nature of fluid mixing and water-rock interactions. Smackover Formation brines exhibit Na-Cl-Ca hydrogeochemical facies and sulfate depletion relative to seawater. Lower sulfate concentrations, coupled with high H₂S concentrations in some brines (0-364 mg/L) at temperatures >80°C, suggest that thermochemical sulfate reduction occurred. Cl/Br and Na/Br ratios indicate that salinity was controlled by the mixing of meteoric water with evaporated seawater that had reached halite saturation, rather than by halite dissolution. The δ¹⁸O and δ²H values of the brines also suggest mixing between meteoric water and evaporated seawater that had reached gypsum and halite saturation. Geochemical modeling of seawater evaporation predicts a Cl-Na or Cl-Mg facies after halite saturation, contrasting with the observed Cl-Ca dominance of the Smackover Formation brines. The Ca-enriched brines may have evolved from Cl-Mg-dominated evaporated seawater through dolomitization of limestone. The ⁸⁷Sr/⁸⁶Sr ratios range from 0.70740 to 0.71048, higher than the average of Jurassic seawater (0.707). The non-linear relationship between ⁸⁷Sr/⁸⁶Sr and 1000/Sr suggests alteration of brine geochemistry by fluid mixing or by inputs from Sr and ⁸⁷Sr-enriched rock sources. Lithium concentrations are positively correlated with ⁸⁷Sr/⁸⁶Sr ratios and TDS in brines enriched in these constituents. These correlations suggest deeper-seated geogenic sources and have implications for Li exploration in the northern Gulf Coast basin. Normal faults associated with the pre-Jurassic topography may have provided potential pathways for brine migration into the Smackover Formation under the influence of overpressure or thermohaline convection in the Gulf Coast.