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  1. A Rapid Decision Support Tool for Estimating Impacts of a Vadose Zone Volatile Organic Compound Source on Groundwater and Soil Gas

    Diminishing rates of subsurface volatile contaminant removal by soil vapor extraction (SVE) oftentimes warrants an in‐depth performance assessment to guide remedy decision‐making processes. Such a performance assessment must include quantitative approaches to better understand the impact of remaining vadose zone contamination on soil gas and groundwater concentrations. The spreadsheet‐based Soil Vapor Extraction Endstate Tool (SVEET) software functionality has recently been expanded to facilitate quantitative performance assessments. The updated version, referred to as SVEET2, includes expansion of the input parameter ranges for describing a site (site geometry, source characteristics, etc.), an expanded list of contaminants, and incorporation of elements of themore » Vapor Intrusion Estimation Tool for Unsaturated‐zone Sources software to provide soil gas concentration estimates for use in vapor intrusion evaluation. As part of the update, SVEET2 was used to estimate the impact of a tetrachloroethene (PCE) vadose zone source on groundwater concentrations, comparing SVEET2 results to field‐observed values at an undisclosed site where SVE was recently terminated. PCE concentrations from three separate monitoring wells were estimated by SVEET2 to be within the range of 6.0–6.7 μg/L, as compared to actual field concentrations that ranged from 3 to 11 μg/L PCE. These data demonstrate that SVEET2 can rapidly provide representative quantitative estimates of impacts from a vadose zone contaminant source at field sites. Finally, in the context of the SVE performance assessment, such quantitative estimates provide a basis to support remedial and/or regulatory decisions regarding the continued need for vadose zone volatile organic compound remediation or technical justification for SVE termination, which can significantly reduce the cost to complete for a site.« less
  2. Iodate interactions with calcite: implications for natural attenuation

    Solid-phase interactions and speciation are important to radioiodine transport in groundwater. At the Hanford Site in Southeastern Washington State, iodate (IO3-) is the main aqueous species in dilute radioiodine groundwater plumes. Like other oxyanions, IO3- may be incorporated into and/or adsorbed onto calcite, a common mineral at Hanford, decreasing its mobility in the environment. A series of macroscale batch experiments combined with solid phase characterization were conducted to identify variables impacting time-dependent aqueous IO3- removal via calcite precipitation and determine the location of IO3- within the calcite crystal structure. Results demonstrated 11.5-97% aqueous IO3- removal during initial rapid calcite precipitation.more » Incorporation was apparently the main removal mechanism, although later slower precipitation and/or adsorption may have also contributed to IO3- removal. Using a higher concentration of the calcite forming solutions (i.e., using 1M vs. 0.1M concentrations) resulted in an increase in the amount of precipitated calcite and a greater percentage of IO3- removed; however, calcite formed with lower molarity solutions resulted in higher IO3- mass (µg/g) removal. Solubility testing of laboratory produced calcites showed only small differences in solubility for calcite with and without IO3- incorporated into the structure. Evidence collected from SEM/FIB and TEM/SAED suggested that the IO3- incorporated into calcite was present in regions close to surface (implying potential easy release upon calcite dissolution).« less
  3. A review of the behavior of radioiodine in the subsurface at two DOE sites

    The 129I isotope has a half-life of nearly 16 million years, creating a potential risk to receptors when 129I is present in groundwater and effective remedies are needed to mitigate its potential risk in the environment. This paper not only provides an in-depth review of various processes and reactions that control the fate and transport of iodine, but also describes how this information can be used for in situ management of iodine. The majority of the iodine fate and transport studies have been conducted at the US Department of Energy (DOE) Hanford and Savannah River sites, where radioisotopes of iodinemore » were inadvertently released into the environment during weapons production. Site-specific remediation technologies are currently being evaluated as part of the DOE cleanup mission. The sites are markedly different in terms of climate (arid vs. sub-tropical), major geochemical parameters (pH ~ 7.5 vs. 4) and mineralogy (carbonate vs. Fe/Al oxide dominated), but they share the same network of processes and reactions that control iodine fate and transport. These include adsorption to minerals and sediments, interactions with organic matter, electron transfer reactions with minerals and microbes, and precipitation. In conclusion, this process-based network serves as basis for regional scale model calculations to predict plume spreading and/or dissipation, design efficient remediation techniques and conduct contamination management activities.« less
  4. Performance Assessment of Pump-and-Treat Systems

    Pump-and-treat (P&T) is a widely applied remedy for groundwater remediation at many types of sites for multiple types of contaminants. Decisions regarding major changes in the remediation approach are an important element of environmental remediation management for a site using P&T. While existing guidance documents provide information on design, operation, and optimization for P&T systems, these documents do not provide specific technical guidance to support remedy decisions regarding when to transition to a new remedy or to initiate closure of the P&T remedy. A structured approach for P&T performance assessment was developed and is described herein, using analysis of threemore » example P&T systems. These examples highlight key aspects of the performance assessment decision logic and represent assessment outcomes associated with optimizing the P&T system, transitioning from P&T to natural attenuation, and supplementing P&T with another technology to hasten transition to natural attenuation.« less
  5. Uranium fate in Hanford sediment altered by simulated acid waste solutions

    Many aspects of U(VI) behavior in sediments that are previously exposed to acidic waste fluids for sufficiently long times to induce significant changes in pH and other physical, mineralogical and chemical properties, are not well documented in the literature. For this reason, we conducted a series of macroscopic batch experiments combined with a variety of bulk characterization studies (Mössbauer and laser spectroscopy), micro-scale inspections (µ-XRF), and molecular scale interrogations (XANES) with the objectives to: i) determine the extent of U(VI) partitioning to Hanford sediments previously exposed to acidic waste simulants (pH = 2 and pH = 5) and under neutralmore » conditions (pH = 8) at varying background solution concentrations (i.e., NaNO3); ii) determine micron-scale solid phase associated U valence state and phase identity; and iii) provide information for a plausible conceptual model of U(VI) attenuation under waste plume acidic conditions. The results of the batch experiments showed that the acid pre-treated sediment had high affinity for aqueous U(VI), which was removed from solution via two pH dependent and apparently different mechanisms (adsorption at pH = 2 and precipitation at pH = 5). The micro-scale inspections and XANES analyses confirmed that high concentration areas were rich mainly in U(VI), demonstrating that most of the added U(VI) was not reduced to U(IV). The laser spectroscopy data showed that uranyl phosphates {e.g. metaautunite [Ca(UO2)2(PO4)2•10-12H2O] and phosphuranylite [KCa(H3O)3(UO2)7(PO4)4O4•8(H2O)]} were present in the sediments. They also showed clear differences between the U bearing phases in the experiments conducted in the presence or absence of air. As a result, the data generated from these experiments will help in a better understanding of the reactions and processes that have a significant effect and/or control U mobility.« less
  6. Measuring Spatial Variability of Vapor Flux to Characterize Vadose-zone VOC Sources: Flow-cell Experiments

    A method termed vapor-phase tomography has recently been proposed to characterize the distribution of volatile organic contaminant mass in vadose-zone source areas, and to measure associated three-dimensional distributions of local contaminant mass discharge. The method is based on measuring the spatial variability of vapor flux, and thus inherent to its effectiveness is the premise that the magnitudes and temporal variability of vapor concentrations measured at different monitoring points within the interrogated area will be a function of the geospatial positions of the points relative to the source location. A series of flow-cell experiments was conducted to evaluate this premise. Amore » well-defined source zone was created by injection and extraction of a non-reactive gas (SF6). Spatial and temporal concentration distributions obtained from the tests were compared to simulations produced with a mathematical model describing advective and diffusive transport. Tests were conducted to characterize both areal and vertical components of the application. Decreases in concentration over time were observed for monitoring points located on the opposite side of the source zone from the local–extraction point, whereas increases were observed for monitoring points located between the local–extraction point and the source zone. We found that the results illustrate that comparison of temporal concentration profiles obtained at various monitoring points gives a general indication of the source location with respect to the extraction and monitoring points.« less

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