Crude oil in a shallow sand and gravel aquifer-I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed ∼1 pH unit, and the concentrations of Ca, Mg and HCO₃^- increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO₂, Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO₂ precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix. The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.