Arsenic Occurrence, Mobility, and Retardation in Sandstone and Dolomite Formations of the Fox River Valley, Eastern Wisconsin

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Abstract
Elevated levels of groundwater arsenic (∼100 μg L-1 = 1.3 × 10-6 M) are found in the Fox River Valley, eastern Wisconsin. The goals of this study were to identify the sources of As contamination and to determine the reactions responsible for As mobilization and retardation in areas lacking a discrete zone of As-enriched sulfides, shown previously to cause elevated arsenic in groundwater. Detailed mineralogical and chemical analyses were conducted on samples from the Sinnipee Group dolomite and St. Peter sandstone in eastern Wisconsin. Solution chemistry was monitored in batch reactions of dolomite, quartz, and sulfide mineral fractions with a 0.01 M CsCl solution at pH 7 for 3 weeks in air. Results indicate that arsenic is present in isomorphous substitution with pyrite/marcasite (FeS2), which occurs as disseminated veins, grains, and nodules in the dolomite and sandstone. The released As sub- sequently sorbs on the ferric oxyhydroxides formed or coprecipitates in a scorodite-like phase. Significantly, oxidative dissolution of the disseminated As-rich FeS2 grains and nodules is sufficient to explain the elevated As levels observed in eastern Wisconsin groundwater. Although complete uptake of As is observed in the batch experiments, persistent elevated As levels with spatial and temporal variations in regional groundwaters are attributed to differences in the type of sulfide occurrence (discrete horizon vs dispersed grains, veins, and nodules), variations in the dissolved oxygen content of the groundwater, and variable (limited) buildup of reacted surface layers on sulfide grains in the natural flow-through system. Discrete nanoparticulate As phases, As surface precipitates on sulfides, and sorbed As on dolomite and quartz are eliminated as major sources, and sorption of arsenic on dolomite and quartz is deemed less important than association with ferric oxyhydroxides for retardation in the regional system.