Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain, USA

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ∼300 km long. The hydrochemical facies evolves from Ca-HCO₃ upgradient to Na-HCO₃ downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO₄ ²⁻ reduction to methanogenesis. In particular, decreasing SO₄ ²⁻ and increasing δ³⁴S of SO₄ ²⁻ along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO₄ ²⁻ reduction. Values of δ¹³C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH₂O oxidation, and dissolution of amorphous Fe(OH)₃, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.