Engineering topics

Bagwell, Christopher E.

Publications and source records attributed to Bagwell, Christopher E..

At least 19 records

DOE OSTI2026

Carbon Tetrachloride Degradation Results for 200-ZP-1 Operable Unit

Carbon tetrachloride (CT) contamination in the 200-ZP-1 Operable Unit (OU) at the Hanford Site originated from large-volume discharges to the subsurface during plutonium production operations between 1955 and 1973. Contamination migrated through more than 70 meters of unsaturated sediment to reach the underlying unconfined aquifer, where it persists as a large and complex groundwater plume. The 200-ZP-1 OU Record of Decision (ROD) requires that groundwater CT concentrations be reduced to 3.4 µg/L within 125 years. Current groundwater modeling projections estimate that the existing pump-and-treat, even when combined with monitored natural attenuation (specifically hydrolysis), will not achieve this target within the designated timeframe. A fundamental contributor to this shortfall is the extremely slow rate of CT hydrolysis under Hanford aquifer conditions, which has been estimated to have a half-life of 630 years. If faster-acting biotic and abiotic degradation processes are operating within the aquifer, their contribution to CT mass reduction could have a meaningful impact. However, site-specific measurements of these processes and their rates have not previously been performed. This report documents the results of a two-phase laboratory investigation designed to characterize and quantify the capacity of site-specific 200-ZP-1 OU sediments and groundwater to support natural attenuation of CT through biotic and abiotic pathways. In this context, degradation capacity is defined as the intrinsic potential of the subsurface matrix to transform CT under optimized, controlled conditions. System capacity is evaluated in two ways: (1) as rate-limited capacity, which establishes the maximum kinetic velocity of CT transformation and is measured using half-lives and first order rate constants; and (2) as mass limited capacity, which defines the total contaminant mass the batch experimental system can degrade before reactants are exhausted, representing the maximum amount of contaminant the microbial community and reactive mineral phases can transform under the experimental conditions.

abiotic degradation↗

DOE OSTI2026

Beyond Component Optimization: Systems Level Biodesign for Lanthanide Recovery

Global demand for lanthanides (Ln) is projected to rise sharply over the next decade, while geographically concentrated supply chains and the low concentrations and matrix complexity of secondary feedstocks limit the reach of conventional hydro- and pyrometallurgical separation. Engineered biological systems offer a selective, low-energy alternative, and component-level advances in Ln-binding proteins, AI-designed selective scaffolds, and cell-surface display platforms now rival synthetic chelators in affinity and selectivity. These components, however, remain functionally isolated. Currently, there are no engineered chassis coupling recognition, intracellular trafficking, accumulation, and controlled release into an end-to-end pipeline. Here, we outline how new biodesign strategies and chassis selection must move beyond bioleaching to encompass the full recovery pathway. Achieving this requires integrating AI/ML-guided design, genome-scale build tools, high-throughput phenotyping, and biophysical transport modeling within a Design–Build–Test–Learn cycle tuned to recognition, trafficking, accumulation, and release.

Biodesign↗

DOE OSTI2026

Enhanced Recovery of Critical Minerals and Geological Hydrogen in The Mine of the Future

invited perspective article: The rapid demand for critical minerals (CMs) and hydrogen (H2) necessitates innovative solutions beyond conventional mining. This study explores enhanced mineral recovery (EMR) and geological hydrogen production (GeoH2) by leveraging the Earth’s subsurface as a reactive platform. Using ultramafic rocks and engineered fluids, the approach simultaneously mobilizes critical resources and produces H2 through natural processes like serpentinization. This paradigm offers a transformative pathway to secure essential materials and diversify energy resources, setting a foundation for the Terrestrial Mine of the Future

Yan, Keju↗

DOE OSTI2025

Uptake of technetium and iodine (I−, IO3− and organo-I) by pecan biochar

Not Available

Lin, Peng↗

DOE OSTI2024

Microbial Analysis of 100-N Borehole Samples: Estimation of Diesel and BTEX Degrading Bacterial Populations

Historical unplanned releases at the UPR-100-N-17 166-N Diesel Oil Supply Line Leak waste site located within the 100-NR-1 OU resulted in diesel fuel contamination of the unsaturated vadose zone and site groundwater. Enhanced in situ bioremediation of the deep vadose zone was the final remedy decision for the 100-NR-1 Operable Unit (OU) and the full-scale bioventing demo began in 2012. For this remedy, oxygen is actively supplied to the deep vadose zone to stimulate aerobic hydrocarbon degrading microorganisms to metabolize petroleum contamination. Degradation rate calculations based on vadose zone respirometry measurements, however, have indicated declining activity over recent years, though the precise reason for this apparent decline has not been determined. In this investigation 100-NR-1 OU sediment cores were analyzed for total microbial biomass, as well as enumeration of diesel and BTEX degrading bacteria to determine if these microbial populations have declined relative to previous measurements taken in 2009.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Nitrate and Nitrite at Hanford – From Tanks to Natural Attenuation

Washington River Protection Solutions, LLC (WRPS) contracted Pacific Northwest National Laboratory (PNNL) in support of their maturation testing and analysis to develop and deploy an ambient temperature solidification/stabilization process for low-activity waste (LAW) (referred to as “grout” in this report). The intent of this effort is to support a sample-and-send regulatory and processing strategy in the Hanford 200 West Area, specifically considering grout waste forms disposal at Hanford in the Integrated Disposal Facility (IDF). Currently the disposal of grouted LAW is not an option because the IDF is not permitted to receive this waste form. The material presented in this report is intended to help inform the U.S. Department of Energy (DOE), the site operating contractors, regulatory agencies, and stakeholders of the future implications of IDF disposal of a grouted LAW waste form, specifically for the behavior of nitrate (NO 3 - ) and nitrite (NO 2 - ) at the Hanford. The only calculation of nitrate release from a hypothetical grouted LAW inventory in the IDF showed that the overall release was slightly above the compliance limit of 45 mg/L nitrate and 3.32 mg/L nitrate after 1000 years (Asmussen et al. 2019). As such, uncertainty around the impact of nitrate and nitrite release from the IDF was identified in the recent National Academies of Sciences study of Hanford supplemental LAW by both the national laboratory team and Hanford stakeholders (Bates et al. 2023). However, these calculations (and others for the IDF involving secondary waste grout) may be conservative as no nitrate and nitrite retention in the grout waste form was assumed, nor any attenuation in the subsurface. There is evidence from the literature of processes that can attenuate nitrate migration both in the waste form and in the Hanford subsurface. If found to be technically defensible and likely to occur in the IDF and associated subsurface, then these processes should be included in modeling of the IDF to represent the behavior of nitrate and nitrite more accurately. Doing so would remove unnecessary conservatism in the modeling projections and reduce the uncertainty in assessments of facility compliance of a grouted LAW waste form in the IDF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

200-DV-1 Laboratory Treatability Study: Proof-of-Principle Results

This document presents the Phase 1 technical approach and results of laboratory-scale treatability testing of nine in situ remedial technologies for their consideration in a future Feasibility Study (FS) for the 200-DV-1 OU. The primary objective of this initial assessment was a proof-of-principle testing evaluation primarily via batch experiments to determine the potential reduction and sequestration of primary contaminants of interest with and without potential co-contaminants of interest. An effectiveness rate of 35% transformation to immobile or nontoxic end products, along with other experimental indicators, was used by the project team to determine the technologies that advanced to Phase 2 for further evaluations. For most technologies, the performance was evaluated based on a series of sequential extractions designed to evaluate the mobility of contaminants before and after treatment, with each subsequent extraction representing a relative decrease in mobility. The results of this study will be used to inform testing for Phase 2 of the treatability study for further evaluation of selected technologies. The final results from the treatability study, following the completion of remaining experimental phases, will be used to determine whether the technologies tested can be appropriately evaluated in a FS to expand on the limited number of viable DVZ remediation technologies. After completion of the laboratory treatability study and the 200-DV-1 OU Remedial Investigation (RI) and Resource Conservation and Recovery Act Facility Investigation (RFI) of the waste sites, results will be evaluated to determine whether field studies are needed to provide additional information on effectiveness, implementability, or costs for evaluating these technologies in the FS for their site-specific application.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Development of Scalable Reactive Transport Framework for PFAS

Research on PFAS chemicals is extensive and covers all aspects, including analytical quantification, determination of properties, toxicology, ex situ treatment, and in situ remediation. PFAS chemicals are very stable and thus persistent/recalcitrant in the environment. Although there are many unknowns about PFAS chemicals, degradation pathways, reaction rates, etc., many different sorption, oxidation, reduction, biological, and innovative treatment approaches are being developed. Sorption with activated carbon is currently the only fully available in situ treatment technology for PFAS-impacted groundwater. Given the wide array of PFAS chemicals and transformation products, remediation may need multi-step treatment trains to fully address the PFAS contamination. The work here provides kinetic reaction modules that represent an initial cut at functionality representing PFAS migration and reaction in groundwater aquifer flow and transport models. One reaction kinetics module provides a method to model kinetically limited adsorption using a mass transfer model. The second reaction module represents biological transformation of 8:2 FTOH and daughter species, illustrating how a complex reaction pathway network can be represented. Both reaction modules allow for spatially variable parameter values so that a variety of remediation approaches (e.g., a PRB or volumetric treatment or variations in geochemical conditions) can be simulated. The intent with these PFAS reaction modules is to provide tools for practitioners to aid in the selection, design, and assessment of potential in situ PFAS remediation strategies. It is anticipated that, as PFAS remediation technologies and scientific understanding advances, these modules would be refined or replaced to match new knowledge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Characterizing the Influence of Organic Polymers on the Specific Reactivity of Particulate Remedial Amendments

Commercially available particulate amendments demonstrate high reactivity for effective treatment of water soluble organic and inorganic contaminants in laboratory studies; however, transport of these particles is constrained in the subsurface. In many field applications, particulate amendments are mixed with organic polymers to enhance mobility for direct push applications or stabilize suspensions for high mass loadings. As such, the interactions between particulate amendments, organic polymers and contaminant species need to be systematically investigated to properly understand mechanistic processes that facilitate predictive performance metrics for specific applications in situ . In this study, batch experiments were conducted to quantify the effects of organic polymers (xanthan gum, guar gum, and sodium alginate), polymer concentration (800 and 4,000 mg/L), and aging (up to 28 days) on chromate treatment rate and capacity by two classes of amendments: reductants [granular zero-valent iron (gZVI), micron-ZVI (mZVI), sulfur modified iron (SMI)], and an adsorbent (bismuth sub-nitrate). When particulate amendments were suspended in polymer solutions, reductants retained between 84–100% of the amendment treatment capacity. Conversely, the adsorbent maintained 63–97% relative treatment capacity of the no-polymer control. Polymer solutions had a more pronounced impact on the rate of chromate removal; first order rates of chemical reduction decreased by as much as 70% and adsorption by up to 81% relative to the no-polymer controls. Polymer–amendment aging experiments also showed decreased Cr(VI) treatment capacity; reductants decreased by as much as 24% and adsorption decreased by as much as 44% after 28 days of incubation. While polymer suspensions are needed to aid the injection of particulate amendments into the subsurface, the results from this study indicate potential losses of treatment capacity and a decrease in the rate of remedial performance due to the physical and chemical interactions between polymer suspensions and reactive particulate amendments. Simple batch systems provide baseline characterization of tripartite interactions for the removal of Cr(VI). Additional work is needed to quantify the full impact of polymers on remedial outcomes under site relevant conditions at field scale.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Guidance for Monitoring Passive Groundwater Remedies Over Extended Time Scales

Passive remediation can be appropriate where natural processes and actions such as institutional controls mitigate exposure to contaminated groundwater, achieving remedial action objectives and protectiveness of human health and the environment. Monitored natural attenuation (MNA) is a prevalent passive remediation strategy supported by a regulatory framework and monitoring design guidance. However, long-term passive remedies are usually selected in combination with at least one active remedy, such as source removal, in situ treatment, or pump-and-treat, functioning as a complementary method for achieving remediation objectives and meeting the applicable statutory and regulatory requirements. However, MNA and existing monitoring guidance primarily target situations where the remedial action objectives are met within a few decades. When time scales for passive remediation extend to many decades (50 years or more), a corresponding change in monitoring strategy is needed to adapt to the extended time scale. This document provides guidance for implementing an extended-scale monitoring (ESM) approach appropriate for long-duration passive remediation. Extended-scale is defined in this document with respect to time (i.e., a long duration of remediation) and a large enough physical scale such that downstream receptors will not be impacted within the remediation timeframe. ESM applies to slow-moving groundwater contaminant plumes and emphasizes monitoring primarily for potential exposure pathways. For this approach, the primary monitoring objective is to demonstrate that the plume diminishes before reaching the receptor zone or point of compliance and/or a receptor does not receive concentrations above the compliance limit. While the overall objectives of protecting human health and the environment are the same as for plumes where remediation can occur over a shorter time period, the time scales between decisions are longer and the dynamics of plume evolution are slower. To this end, a scenario-based strategy is described for different plume and source conditions, defining a containment and receptor zones. The containment zone is the area where the risk of exposure to groundwater contamination can be mitigated (e.g., through institutional controls) during the remediation time period. The receptor zone is defined as the area where exposure to groundwater contamination cannot be mitigated and compliance concentration standards must be met. Within the containment zone, slow plume migration may occur, leading to concentrations that exceed compliance standards. However, where distance to the receptor zone is large relative to plume migration and attenuation rate, this approach can be protective of the receptor zone. Selection of a long-duration passive remedy needs to be based on sufficient understanding of contaminant sources, hydrogeology, and contaminant plumes. A strong technical basis, supported by predictive analysis, is recommended to substantiate that contamination is expected to stay within the containment zone during the active remediation and attainment phase of the remedy, and diminish to meet compliance standards within the extended timeframe prior to reaching the receptor zone (e.g., many decades or even centuries). The ESM approach is based on verification of plume behavior and not on detailed plume dynamics. Monitoring is conducted to confirm expected behavior with an emphasis on exposure pathways to verify that plumes remain contained in areas where the protectiveness objectives can be met. ESM should not be adopted if there is significant risk of the plume extending beyond the containment zone. Given the slow movement within the containment zone, less frequent sampling is required relative to approaches used for conventional-scale remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Analysis of Microbial Communities as Indicators of Microbially Induced Corrosion Potential in Stainless Steel Piping

The 200 West Area Pump-and-Treat (200W P&T) facility is part of the final remedy decision for the 200 ZP-1 Operable Unit (OU) and is the interim remedial action for 200-UP-1 OU at the Hanford Site. The facility also treats water from other sources across the site, including 200-DV-1 OU perched water, groundwater from the 200-BP-5 OU, and leachate from the Environmental Restoration Disposal Facility. The facility originally operated a biological treatment process for nitrate that resulted in systemic biofouling and loss of injection well capacity, requiring frequent and costly well rehabilitation. Biofouling has also contributed to corrosion of welds and pitting of stainless-steel piping at the facility. The biological treatment for nitrate was suspended at the end of 2019 calendar year to eliminate negative impacts from biological treatments which improve facility operations and treatment of carbon tetrachloride. Evaluation of the 200W P&T facility’s response to operational improvements, specifically the suspension of the biological treatment, provides information on the potential for continued microbially induced corrosion (MIC). To this end, historical data sets (2015-2017) were compared with molecular biological analyses of 200W P&T water samples from 2018-2020 to quantify trends in total microbial biomass and specific microbial indicator species (iron, sulfate, nitrate, and manganese reducing bacteria) known to cause and enhance metal corrosion. Results showed unequivocal reductions (in excess of 90%) in all microbiological indicators measured following the suspension of the biological treatment. Although abundance measurements for all corrosive MIC populations initially declined after removal of the treatment system, nitrate-reducing bacteria (nirK) and sulfate-reducing bacteria remain highly abundant in the system, an order of magnitude higher than the number of cells present prior to the removal of the biological treatment system [5.14e (1.4) cells/L, vs. 1.14e (0.07) cells/L, reported as average (±SD) for n=3]. In addition, there was an unexpected inflection point in 2019 where all microbial indicators increased unexpectedly in abundance in 2020 by as much as two orders of magnitude compared to 2019 samples. Given the limited number of water samples available for this analysis, the cause of the increase in microbial indicators post-biological treatment has not yet been determined. Systematic sampling of the facility for continued monitoring is recommended so that the responses of MIC populations can be evaluated to ensure that further corrosion is avoided, allowing the 200W P&T facility to operate safely and efficiently at design capacity.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Combined Technologies for In Situ Remediation of Tc-99 and U in Subsurface Sediments

In this study, combinations of chemical remedies were tested in bench-scale batch experiments to evaluate a two-step reduction-sequestration approach to effectively stabilize high concentrations of inorganic contaminant mixtures. Bench tests simulated contaminant and geochemical conditions of a perched aquifer located within the Central Plateau at the Hanford Site, located in southeastern Washington State (USA). Pairwise combinations of a reductant [e.g., zero valent iron, sulfur modified iron (SMI), or calcium polysulfide] and a sequestering agent [e.g., calcite, apatite, or dilute alkaline solution (e.g., NaOH)] were evaluated for immobilization and stabilization of technetium (Tc) (50,000 pCi/L), uranium (U) (150 mg/L), and nitrate (NO 3 ) (200 mg/L) in high ionic strength groundwater. The results of these batch studies demonstrated that reduction by SMI and sequestration in apatite or calcite are the most effective combination for these contaminant mixtures and conditions. Aqueous concentrations of Tc and U decreased by 95.6% ± 2.5% and 101.1% ± 5.2%, respectively, with SMI-apatite and 98.3% ± 0.0% and 101.2% ± 5.2%, respectively, with SMI-calcite. Sequential extractions showed that sequestered contaminants had limited capacity for re-oxidation; in fact, less than 10% of immobilized Tc and U was recovered by selective extraction of mineral phases most susceptible to oxidation. In addition, X-ray absorption near edge structure analysis of the sediment samples treated with SMI-calcite showed the presence of only U(IV), while both U(IV) and U(VI) were present in the SMI apatite combination [ratio of 0.43 U(IV):0.59 U(VI)].This study describes preliminary results that a two-step approach for stabilizing contaminant mixtures of long-lived radionuclides can be effective at reducing contaminant fluxes to groundwater from vadose and perched water zones.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Methods for Delivery and Distribution of Amendments for Subsurface Remediation: A Critical Review

The ability to reliably deliver and widely distribute remedial amendments through the subsurface environment is of paramount importance to achieve clean-up objectives for contaminated sediments and groundwater for protection of sensitive environmental habitats and natural resources. A wide range of amendment types, delivery techniques, and subsurface access methods are available. However, the applicability of these approaches is dependent on a multitude of site-specific factors and conditions. In this review, an overview of amendment types (i.e., liquid, gas, and solids) and access/distribution methods is provided, along with discussion of the maturity level (low, medium, or high), advantages, and limitations that relate to the potential effectiveness of each approach in the context of site-specific factors (subsurface geology, geochemistry, contaminant properties, etc.). Each amendment type and delivery approach are further evaluated for applicability to the following subsurface target zones: saturated, unsaturated, and perched water, with specific focus on high and low permeability variants of each zone. The review highlights a critical need for field-tested approaches targeting unsaturated and perched water zones, as well as low-permeability regions within all subsurface regions. The intent of this review is to provide critical information and insight into how amendments can be delivered, emplaced, and/or distributed effectively in the subsurface environment to effectively manage subsurface contamination.

Muller, Katherine A.↗

DOE OSTI2020

Guidance for Monitoring Passive Groundwater Remedies Over Extended Time Scales

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Evaluation of Ammonia Discharge into PUREX Crib 216-A-37-1 and Nitrogen Species Fate in the Subsurface

Based on published data, this report identifies potential fate and transport mechanisms for the ammonium hydroxide condensate that was discharged to 216-A-37-1 Crib from Hanford fuel rod decladding before PUREX dissolution and separation operations. Crib 216-A-37-1 received 377 million liters of alkaline condensate discharged from March 1977 through April 1989. The following major processes were identified as controlling the ammonia (NH 3 ) fate and transport: 1. Liquid migration rates through the vadose zone 2. NH 3 microbial oxidation to nitrite and nitrate 3. Ammonia species [NH4 + , NH 3 (aq)] sorption to sediments 4. NH3 precipitation reactions after pH buffering occurs in sediments The travel time through the vadose zone was estimated to be 2.5 to 9 months during periods of high subsurface discharge rates. These travel times are based on tritium migration through the vadose zone, a co-contaminant also discharged to the 216-A-37-1 crib.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Biotic degradation of acetonitrile. Limitations, controls and conversion rates

This document has been prepared to support Washington River Protection Solutions (WRPS) in their evaluation of technologies to remediate organic compounds in the Liquid Effluent Retention Facility (LERF)/Effluent Treatment Facility (ETF) during direct feed low activity waste (DFLAW) operations at Hanford. This report summarizes the results of a review of the available literature describing aerobic and anaerobic biological treatment of acetonitrile and proposes a test matrix to evaluate microbial degradation rates of acetonitrile. Numerous studies describe acetonitrile degradation by pure culture strains of bacteria, fungi, and yeast; however, the purpose of this review was to provide estimations of degradation under conditions that more closely approximate the Liquid Effluent Retention Facility (LERF) basins at the Hanford Site. To this end, documented limitations, controls, and conversion rates are summarized for mixed and natural microbial communities being maintained or operated as a biological treatment for wastewater processing. Based on the literature evaluation, the inherent capacity and rates of microbial degradation of acetonitrile are sufficiently high that if applied in the LERF basins, acetonitrile removal would be achieved. To be clear, though, published studies have not been conducted under conditions that approximate or that could be directly related to the LERF basins. Thus, a focused test matrix the encompasses LERF relevant conditions to specifically measure microbial degradation of acetonitrile is proposed and the results would provide the strong technical justification for use of this low-cost efficient biological process at LERF during DFLAW operations and beyond.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Evaluation of Gaseous Substrates for Microbial Immobilization of Contaminant Mixtures in Unsaturated Subsurface Sediments

Extensive vadose zone metals and organic contamination remains at many former industrial and defense manufacturing sites, and effective remedial solutions are needed to slow or prevent its migration to groundwater. In this study, the application of gaseous substrates to stimulate microbial respiratory reduction of comingled radioisotopes and nitrate under unsaturated conditions was examined for possible application at the Hanford Site, a former nuclear production facility in southeastern WA, USA. First, screening studies were performed to qualitatively measure the sediment respiratory response to 14 gaseous or volatile organic substrates at two moisture contents, 4% and 8%. Volatile substrates produced the strongest respiratory response, among them were butyrate, pentane, butyl acetate. Ethane and butane were the most effective gaseous substrates but only at 8% water content. Hanford sediment from two waste sites with distinctive chemistries were wetted to 7% moisture content, packed into columns, and treated with ethane or butane. After 4 weeks, columns were then leached to quantify retardation in the mobility of aqueous contaminant concentrations compared to no gas control columns. Treatment with both gases resulted in >80% removal of Cr from the aqueous phase. However, NO3 concentration and a waste sites exposure history to NO3 had a major effect on U and Tc reduction. Incomplete nitrate reduction outcompeted U and Tc in waste site sediments having limited prior exposure to NO3. Conversely, waste site sediments co-contaminated with NO3 were able to achieve highly reduced conditions resulting in complete denitrification of NO3, and delayed leaching of U and Tc. This implied effective reduction of both contaminants to less mobile species. This study demonstrates that unsaturated vadose sediments at Hanford waste sites have the capacity for a sustained respiratory response to gaseous substrate injection, which could potentially be deployed as part of an overall strategy to reduce the flux of long-lived radionuclides to groundwater at Hanford and other legacy waste sites.

Bagwell, Christopher E.↗