Alexandre V. Mitroshkov

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.14, 4.16, 5.20, 5.22, 5.43, and 5.45. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples.

Carbon Tetrachloride and Chloroform Partition Coefficients Derived from Aqueous Desorption of Contaminated Hanford Sediments

Researchers at PNNL determined CCl4 and CHCl3 groundwater/sediment partition coefficients (Kd values) for contaminated aquifer sediments collected from borehole C3246 (299-W15-46) located in the 200 West Area adjacent to the Z-9 trench. Having realistic values for this parameter is critical to predict future movement of CCl4 in groundwater from the 200 West Area.

Noble gas migration experiment to support the detection of underground nuclear explosions

A Noble Gas Migration Experiment injected 127Xe, 37Ar, and sulfur hexafluoride into a former underground nuclear explosion shot cavity. These tracer gases were allowed to migrate from the cavity to near-surface and surface sampling locations and were detected in soil gas samples collected using various on-site inspection sampling approaches. Based on this experiment we came to the following conclusions: (1) SF6 was enriched in all of the samples relative to both 37Ar and 127Xe. (2) There were no significant differences in the 127Xe to 37Ar ratio in the samples relative to the ratio injected into the cavity. (3) The migratory behavior of the chemical and radiotracers did not fit typical diffusion modeling scenarios.

Desorption behavior of carbon tetrachloride and chloroform in contaminated low organic carbon aquifer sediments

Slow release behavior of carbon tetrachloride (CCl(4)) and chloroform (CHCl(3)) in low organic carbon (<0.1%) deep aquifer sediments was quantified by 1-D column desorption studies with intact cores. The compounds had been in contact with the sediments for 30years. Comparison of the CCl(4) distribution coefficient (K(d)) from this study with those from short contact time experiments suggested that CCl(4)K(d)s calculated from site contaminated sediments of long contact time are likely a factor of 10 or more higher than those calculated from short contact-time lab experiments. A significant portion of the CHCl(3) mass (55% to more than 90%) was resistant to aqueous desorption in sediments with clay contents ranging from 2.0% to 36.7% and organic carbon content ranging from 0.017% to 0.088%. In contrast, CCl(4) showed greatest mass retention (31% or more) only in the highest clay and organic carbon content sediment. Relatively easy solvent extraction of the residual masses of CCl(4) and CHCl(3) from the sediments indicated the compounds were not permanently sequestered. Tracer breakthrough in columns was well behaved, indicating interparticle diffusion was not causing the slow release behavior. Diffusion out of intraparticle pores is suggested to be the main process governing the observed behavior although, diffusion out of natural organic matter cannot be ruled out as a potential contributing factor. The half-life for release of the slow fraction of CHCl(3) mass from sediments was estimated to be in the range of weeks (100h) to months (1100h). Neither CCl(4) or CHCl(3) were detected at measurable levels in the column effluent of one of the sediments even though a significant mass fraction of CHCl(3) was found present on the sediment following desorption suggesting that our estimate of hundreds to thousands of hours for complete release of CHCl(3) masses from such sediment is conservative.

Carbon Tetrachloride Partition Coefficients Measured by Aqueous Sorption to Hanford Sediments from Operable Units 200-UP-1 and 200-ZP-1

Kd values obtained on sediment samples from 200-UP-1 and 10-ZP-1 contribute to a larger Kd database that exists for other Hanford sediments, and contains significant desorption data for CCl4. Adsorption results presented here validate the use of a linear adsorption isotherm (Kd) to predict short contact time CCl4 adsorption to sediments in 200-UP-1 groundwater plume for a distinct ranges in CCl4 concentration. However, this does not imply that values of Kd will be constant if the groundwater chemical composition at 200-UP-1 changes with space or time. Additionally, results presented here suggest the potential significance of slower intraparticle diffusion on the long-term fate of CCl4 within the subsurface Hanford environment. Such behavior could afford prolonged desorption of CCl4 and serve as a long-term source of contaminant CCl4 to the aquifer. Further evaluation of possible bimodal sorption behavior for CCl4 and the mechanism of CCl¬4 sequestration should be the subject of future investigations to provide a thorough, mechanistic understanding of the retention and long-term fate of CCl4. Comparison of previous data with new results (e.g., from this study) will allow inferences to be made on how the 200-UP-1 Kd values for CCl4 may compare with sediments from other Hanford locations. This site-specific sorption data, when complemented by the chemical, geologic, mineralogic, hydrologic, and physical characterization data that are also being collected (see Sampling and Analysis Plan for the 200-UP-1 Groundwater Monitoring Well Network, DOE 2002) can be used to develop a robust, scientifically defensible data base to allow risk predictions to be generated and to aid in future remediation decisions for the 200-UP-1 and 200-ZP-1 operable units.

Estimation of the formation rates of polyatomic species of heavy metals in plutonium analyses using a multicollector ICP-MS with a desolvating nebulizer

Analyses of International Atomic Energy Agency (IAEA) and environmental samples for the Pu isotopic content are conducted normally at very low concentrations of Pu—usually in the range of parts per trillion and even more often at the parts per quadrillion level. To analyze such low concentrations, the interferents in the analytical solution must be reduced as much as possible. Polyatomic interferents (PIs), formed by heavy elements (HEs) from Hf to Bi, are known to create problems for Pu isotopic analyses, because even the relatively high resolution of a modern multicollector (MC) inductively coupled plasma-mass spectrometer (ICP-MS) is insufficient to separate Pu isotopes from such PIs in most cases. Desolvating nebulizers (DSNs) (e.g., APEX and AridusII) reduce significantly the formation of PIs compared to the use of wet plasma. The purpose of this work was to investigate the rate of PI formation produced by HMs when a high-resolution (HR) MC-ICP-MS with a DSN was used for Pu isotopic analyses and to estimate the influence of the HEs present in the sample on the results of the analyses. The NU Plasma HR MC and AridusII DSN were used in this investigation. This investigation was done for the interferents for all Pu isotopes normally analyzed by ICP-MS, including 244Pu, with the exception of 238Pu, which most of the time cannot be analyzed using an ICP-MS, because of the overwhelming presence of 238U in the solutions. The PI formation rates were determined and reported. Selected IAEA samples were scanned for the presence of HEs and the influence of HEs on the results of Pu isotopic analyses was evaluated.

Hanford 100-D Area Biostimulation Treatability Test Results

Pacific Northwest National Laboratory conducted a treatability test designed to demonstrate that in situ biostimulation can be applied to help meet cleanup goals in the Hanford Site 100-D Area. In situ biostimulation has been extensively researched and applied for aquifer remediation over the last 20 years for various contaminants. In situ biostimulation, in the context of this project, is the process of amending an aquifer with a substrate that induces growth and/or activity of indigenous bacteria for the purpose of inducing a desired reaction. For application at the 100-D Area, the purpose of biostimulation is to induce reduction of chromate, nitrate, and oxygen to remove these compounds from the groundwater. The in situ biostimulation technology is intended to provide supplemental treatment upgradient of the In Situ Redox Manipulation (ISRM) barrier previously installed in the Hanford 100-D Area and thereby increase the longevity of the ISRM barrier. Substrates for the treatability test were selected to provide information about two general approaches for establishing and maintaining an in situ permeable reactive barrier based on biological reactions, i.e., a biobarrier. These approaches included 1) use of a soluble (miscible) substrate that is relatively easy to distribute over a large areal extent, is inexpensive, and is expected to have moderate longevity; and 2) use of an immiscible substrate that can be distributed over a reasonable areal extent at a moderate cost and is expected to have increased longevity.

Review of Mass Spectrometry Data from Waste Tank Headspace Analyses

Numerous analytes have been categorized as tentatively identified compounds (TICs) in air samples from the headspaces of the Hanford Site high-level radioactive waste tanks. The tentative identification of these compounds was based mainly on the agreement between the observed mass spectra and a library of published mass spectra with consideration given to the gas chromatographic conditions and retention times. Many of the TICs were found in a limited number of tanks, were identified by only one laboratory or by one method, and/or were thought to be unlikely components of the waste or its degradation products. Consequently, the mass spectra of selected analytes have been reviewed to determine if their tentative identifications were correct. From our current review of 49 TICs, we found 25 that were misidentified and recommend that 54 of the associated results be flagged as suspect and 22 of the associated results be assigned a different compound name.