Search

Despite the numerous studies on changes within the reservoir following CO

A series of wet chemical extractions and column experiments, combined with electron microprobe analysis (EMPA) and X-ray photoelectron spectroscopy (XPS) measurements, were conducted to estimate the extent of Cr(VI) desorption and determine the mechanism(s) of Cr(VI) attenuation in contaminated and naturally aged (decades) Hanford sediments which were exposed to dichromate and acidic waste solutions. Results from wet extractions demonstrated that contaminated sediments contained a relatively large fraction of tightly-bound Cr. Results from column experiments showed that effluent Cr concentrations were low and only a small percentage of the total Cr inventory was removed from the sediments. EMPA inspections indicated that Cr contamination was spread throughout sediment matrix and high-concentrated Cr spots were absent. XPS analyses confirmed that most surface Cr occurred as reduced Cr(III), which was spatially associated with Fe(III). Collectively, the results from macroscopic experiments and microprobe and spectroscopic measurements demonstrated that reduction of Cr(VI) have occurred in these sediments, limiting dramatically the mass flux from this contaminated source. The most likely mechanism of Cr(VI) reduction is the acid promoted dissolution of Fe(II)-bearing soil minerals and/or their surface coatings, release of Fe(II) in the aqueous phase, abiotic homogeneous and/or heterogeneous Cr(VI) reduction by aqueous, sorbed and/or structural Fe(II), and subsequently, formation of insoluble Cr(III) phases or [Cr(III) Fe(III)] solid solutions. The results from this study will improve our fundamental understanding of Cr(VI) behavior in natural heterogeneous subsurface media and may be used as a basis for developing or selecting potential remedial measures.

The long-term interactions of carbon tetrachloride (CCl4) and chloroform (CHCl3) with sediments that are low in organic matter (OM) are not well studied and documented in the literature. In this study, CCl4 and CHCl3 were mixed with supercritical carbon dioxide (CO2) and loaded onto columns packed with two sediments with low OM content and different textures, to establish contamination and achieve expedited artificial aging. The columns were subsequently leached with a simulated groundwater under hydraulically saturated conditions. Scanning electron microscopy was used to inspect the morphology of sediment single particles, determine the degree of particle association in aggregates and qualitatively estimate porosity and the length of possible diffusional pathways that might affect the overall contaminant desorption rates in sediments with low sorption capacity. Results demonstrated that most of contaminant inventories were rapidly released in the first pore volume of effluent, although a small portion of contaminants’ total mass exhibited time-dependent desorption. The calculated Kd values of CCl4 or CHCl3 partition were negligibly small. The transport behavior of both contaminants was similar and it was simulated well with a distributed (multiple)-rate (DR) statistical model, which accounted for the apparent contaminant mass transfer through diffusional pathways of different lengths, towards the advectivemore » pores. The distribution of contaminant mass between equilibrium and kinetic fractions, the distribution of the individual rate constants, and the average rate constants calculated with the parameters of the γ-distribution function (β and η) of the DR model, were sediments (texture) dependent, indicating that contaminant desorption during the late stage of leaching was driven by concentration gradients (i.e., diffusion) within sediment matrix porosity.« less