Geochemical and hydrologic controls on the mobilization of arsenic derived from herbicide application

The fate and transport of As was examined at an industrial site where soil- and groundwater contamination are derived from the application of As_2O_3 as a herbicide. Application of arsenical herbicides was discontinued in the 1970s and soils in the source area were partially excavated in 2003. Arsenic contamination (up to 280 mg/kg) remains in the source area soils and a plume of As-contaminated groundwater persists in the surficial aquifer downgradient of the source area with maximum observed As concentrations of 1200 μg/L near the source area. The spatial extent of As contamination as defined by the 10 μg/L contour appears to have remained relatively stable over the period 1996–2006; the boundary of the 1000 μg/L contour has retreated over the same time period indicating a decrease in total As mass in the surficial groundwater. In column experiments conducted with source area soil, the As concentrations in the column effluent were comparable to those observed in groundwater near the source area. A substantial fraction of the As could be leached from the source area soil with ammonium sulfate and ammonium phosphate. Exhaustive extraction with background groundwater removed most of the total As. These results indicate that As in the source area soils is geochemically labile. Source area soils are low in extractable Fe, Mn and Al, and characterization by X-ray absorption spectroscopy and electron microscopy indicated that As is present primarily as arsenate sorbed to (alumino)silicate minerals. Batch sorption experiments showed much less sorption on surficial aquifer sediments than on sediments from the Jackson Bluff Formation (JBF), a presumed confining layer. This limited capacity of the surficial aquifer sediments for As sorption is consistent with the similar As contents observed for these sediments within and upgradient of the As plume. The apparent stability of the As plume cannot be explained by sequestration of As within the surficial aquifer. Sorption to JBF sediments may contribute to As sequestration, but As enrichment in JBF sediments within the plume (i.e., as compared with JBF sediments upgradient) was not observed. These results indicate that neither the persistence of As in the source area soils or the apparent stability of the plume of As-contaminated groundwater at this site can be explained by geochemical controls on As mobility. The absence of demonstrable geochemical bases for such observations suggests that possible hydrologic controls should be further investigated at this site