Geochemical Characterization of Chromate Contamination in the 100 Area Vadose Zone at the Hanford Site

The major objectives of the proposed study were to: 1.) determine the leaching characteristics of hexavalent chromium [Cr(VI)] from contaminated sediments collected from 100 Area spill sites; 2.) elucidate possible Cr(VI) mineral and/or chemical associations that may be responsible for Cr(VI) retention in the Hanford Site 100 Areas through the use of i.) macroscopic leaching studies and ii.) microscale characterization of contaminated sediments; and 3.) provide information to construct a conceptual model of Cr(VI) geochemistry in the Hanford 100 Area vadose zone. In addressing these objectives, additional benefits accrued were: (1) a fuller understanding of Cr(VI) entrained in the vadose zone that will that can be utilized in modeling potential Cr(VI) source terms, and (2) accelerating the Columbia River 100 Area corridor cleanup by providing valuable information to develop remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry. A series of macroscopic column experiments were conducted with contaminated and uncontaminated sediments to study Cr(VI) desorption patterns in aged and freshly contaminated sediments, evaluate the transport characteristics of dichromate liquid retrieved from old pipelines of the 100 Area; and estimate the effect of strongly reducing liquid on the reduction and transport of Cr(VI). Column experiments used the < 2 mm fraction of the sediment samples and simulated Hanford groundwater solution. Periodic stop-flow events were applied to evaluate the change in elemental concentration during time periods of no flow and greater fluid residence time. The results were fit using a two-site, one dimensional reactive transport model. Sediments were characterized for the spatial and mineralogical associations of the contamination using an array of microscale techniques such as XRD, SEM, EDS, XPS, XMP, and XANES. The following are important conclusions and implications. Results from column experiments indicated that most of contaminant Cr travels fast through the sediments and appears as Cr(VI) in the effluents. The significance of this for groundwater concentrations would, however, depend on the mass flux of recharge to the water table. adsorption of Cr(VI) to sediments from spiked Cr(VI) solution is low; calculated retardation coefficients are close to one. Calcium polysulfide solutions readily reduced Cr(VI) to Cr(III) in column experiments. However a significant amount of the Cr(VI) was mobilized ahead of the polysulfide solution front. This has significant implications for in-situ reductive remediation techniques. The experiments suggest that it would be difficult to design a remedial measure using infiltration of liquid phase reductants without increasing transport of Cr(VI) toward the water table. The microscopic characterization results are consistent with the column studies. Cr(VI) is found as ubiquitous coatings on sediment grain surfaces. Small, higher concentration, chromium sites are associated with secondary clay mineral inclusions, with occasional barium chromate minerals, and reduced to Cr(III) in association with iron oxides that are most likely magnetite primary minerals. Within the restricted access domains of sediment matrix, ferrous iron could also diffuse from in situ, high-surface-area minerals to cause the reductive immobilization of chromate. This process may be favored at microscale geochemical zones where ferrous iron could be supplied. Once nucleated, micrometer-scale precipitates are favored as growing locales for further accumulation, causing the formation of discrete zones of Cr(III)