Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA)

r a 200 .027 sent add gmail.c Summary Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25–30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (±2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E 03, 2.13E 04, 4.15E 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E 07, respectively. Cation exchange reactions of Ca (4.93E 04 mol) for Na (2.51E 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 lg/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe