Stability of solid-phase selenium species in fly ash after prolonged submersion in a natural river system

Selenium (Se) chemistry can be very complex in the natural environment, exhibiting different valence states (-2, 0, +4, +6) representing multiple inorganic, methylated, or complexed forms. Since redox associated shifts among most of known Se species can occur at environmentally relevant conditions, it is important to identify these species in order to assess their potential toxicity to organisms. In June of 2009, researchers from the US Army Engineer Research & Development Center (ERDC) conducted investigations of the fly ash spilled 6 months previously into the Emory River at the TVA Kingston Fossil Plant, TN. Ash samples were collected on site from both the original ash pile (that did not move during the levee failure), from the spill zone (including the Emory River), and from the ash recovery ditch (ARD) containing ash removed during dredging cleanup operations. The purpose of this work was to determine the state of Se in the spilled fly ash and to assess its potential for transformation and resultant chemical stability from its prolonged submersion in the river and subsequent dredging. Sequential chemical extractions suggested that the river environment shifted Se distribution toward organic/sulfide species. Speciation studies by bulk XANES analysis on fly ash samples showed that a substantial portion of the Se in the original ash pile had transformed from inorganic selenite to a mixture of Se sulfide and reduced (organo)selenium (Se(-II)) species over the 6-month period. μ-XRF mapping data showed that significant trends in the co-location of Se domains with sulfur and ash heavy metals. Ten-d extended elutriate tests (EETs) that were bubbled continuously with atmospheric air to simulate worst-case oxidizing conditions during dredging showed no discernible change in the speciation of fly ash selenium. The enhanced stability of the organo- and sulfide-selenium species coincided with the mixture of the ash material with humic materials in the river, corresponding with notable shifts in the ash carbon- and nitrogen-functionality.