LAUSR

Abstract Arsenic (As) concentrations and speciation were measured in groundwaters from the upper Chicot aquifer in southern Louisiana to: (1) ascertain the geochemical processes responsible for its mobilization into the groundwater; and (2) investigate the fate and transport of As in the aquifer following its mobilization into solution. Ancillary geochemical parameters, including dissolved iron (Fe) concentrations and speciation, major solutes, pH, and alkalinity were also quantified in the groundwaters, along with the mineralogy and geochemistry of the aquifer sediments. Arsenic concentrations as high as 644 nmol kg−1 (48.2 μg kg−1) were measured in the groundwaters, with the arsenite oxyanion (H3AsIIIO30) accounting for ca. 60%, on average, of the total dissolved As, and the remaining ca. 40% consisting of the arsenate oxyanion (i.e., H2AsVO42−). The groundwaters are Na – HCO3 type waters of slightly alkaline pH (8.09 ≤ pH ≤ 8.34), moderately high mineralization (7.3 mmol kg−1 ≤ I ≤ 13.7 mmol kg−1), and high Fe(II) concentrations (18 μmol kg−1 ≤ Fe(II) ≤ 47 μmol kg−1), and thus are compositionally similar to As-affected groundwaters from South and Southeast Asia (e.g., Bangladesh, West Bengal, India, and Vietnam). Groundwaters with the highest As concentrations also have the highest Fe(II) concentrations, which is consistent with reductive dissolution of Fe(III) oxides/oxyhydroxides releasing sorbed or co-precipitated As into the groundwaters. Biogeochemical reactive transport modeling that employs rates laws for microbial respiration indicates that dissimilatory reduction of Fe(III) oxides/oxyhydroxides coupled to organic matter oxidation can explain the high As concentrations along the mid-reaches of the studied flow path. Geochemical analysis of the aquifer sediments further demonstrates that the bulk of the environmentally mobile As in the aquifer is associated with Fe(III) oxides/oxyhydroxides and/or chemisorbed (i.e., inner-sphere surface complexed) onto aquifer mineral surfaces. Model calculations confirm that mobilization of 2–8% of this labile As could support the high As concentrations measured in these groundwaters. Reactive transport modeling coupled to the generalized double-layer surface complexation model predicts that As(III) could be transported ca. 10 km down gradient from the current location of the As “hot-spot” after 150 years, whereas As(V) is predicted to move between 2.4 km and 8.5 km depending on the composition of Fe(III) oxides/oxyhydroxides in the aquifer. Reactive transport modeling also illustrates how retardation and attenuation of As(III) and As(V) along flow paths in aquifer systems is strongly dependent on the type and content of Fe(III) oxides/oxyhydroxides present in the aquifer with higher contents of amorphous to poorly crystalline forms leading to greater retardation and attenuation of both As species. The data and modeling indicate that although As is readily mobilized by microbial reduction of Fe(III) oxides/oxyhydroxides, its tendency to form strong, inner sphere surface complexes on Fe(III) oxides/oxyhydroxides remaining in the aquifer will control the fate and transport of As once released into solution. We suggest that these observations may help explain the “patchy” spatial distributions of As concentrations commonly observed in As-affected aquifers, such as those of South and Southeast Asia.