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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Characterization of Arsenic and Selenium in Coal Fly Ash to Improve Evaluations for Disposal and Reuse Potential (Final Technical Report)

Coal fly ash is a high volume waste material that is discarded in landfills and surface water impoundments across the U.S. and is also widely recycled for a variety of applications. The leaching of potential of contaminants of concern, such as arsenic (As) and selenium (Se), is often the driver of risk assessments for coal ash disposal and reuse. The extent of leachable As and Se depends on several factors related to environmental conditions and fly ash characteristics. Previous studies employed various methods to delineate the concentration, chemical form, and distribution of As and Se in fly ash materials. However, few studies have attempted to directly correlate these properties to mobilization parameters relevant to disposal and reuse. Instead, the coal residuals industries often rely upon standardized leaching protocols that can be laborious or involve hazardous chemicals. The goals of the project were to: 1) Develop and evaluate a characterization protocol that can be used to screen fly ash samples for leachability of As and Se; 2) Characterize As, Se, and associated constituents of fly ash particles at multiple length scales (nanometer to micrometer) to determine if elemental associations differ as a function of the resolution of characterization; and 3) Establish a predictive model for the chemical composition of coal ash produced annually at major U.S. coal fired power facilities on 50-year national coal supply records. For the first objective, we performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic coal regions. For this work, we assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition (LOI) and pH. The results of regression models indicated that major elements (Fe, Ca, Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As, but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash. For the second objective, we utilized nanoscale 2-D imaging (30-50 nm spot size) with the Hard X-ray Nanoprobe (HXN) in combination with microprobe X-ray capabilities (~5 µm resolution) to determine As and Se elemental associations in fly ash particles. Speciation of As and Se was also measured at the nano- to microscale with X-ray absorption spectroscopy. The enhanced resolution of HXN showed As and Se that were diffusely located around or comingled with Ca- and Fe-rich particles. The results also showed nanoparticles of Se attached to the surface of fly ash grains. Overall, a comparison of As and Se species across scales highlights the heterogeneity and complexity of chemical associations for these trace elements of concern in coal fly ash. For the final objective, we developed a predictive model for major element composition of coal ash in reserve at disposal sites of major U.S. coal fired power plants. This model was constructed from coal purchase records of 705 power stations from 1973-2022 and was trained on coal ash composition data showing that coal ash elemental composition is strongly associated with the source of feedstock coal. The model showed regional shifts in the major element contents of ash produced by power plants in the last 50 years, particularly for calcium and iron (expressed as %CaO and %Fe 2 O 3 ), as coal-fired power stations changed their source of coal over this time frame. Our approach enables an estimation of coal ash chemical composition that is stored in waste impoundments at individual power stations. Such information can help delineate the regional market potential for material applications that would utilize coal ash harvested from disposal sites across the U.S.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Pilot-Scale Testing of an Integrated Circuit for the Extraction of Rare Earth Minerals and Elements from Coal and Coal Byproducts Using Advanced Separation Technologies

The primary objective of this project was to develop and demonstrate an integrated pilot-scale circuitry for recovering high-value rare earth elements (REEs) from coal and coal byproducts. The target performance was to produce a mixed REE product with content of at least two percent by weight on a dry mass basis in a cost-effective and environmentally benign manner. During the first nine months of the project period (Phase 2 Budget Period 2), pilot plant construction was completed including all field site startup activities such as permitting, engineering design, procurement/bidding, unit fabrication, site construction, equipment installation, module assembly, safety training, and circuit shakedown. During the remaining 21 months of project period (Phase 2 Budget Period 3), detailed field-testing activities were performed including feedstock sample collection and preparation, exploratory testing, circuit modification, detailed parametric study, and performance optimization. A detailed techno-economic analysis was performed based on the pilot plant testing findings which provided various scenarios for REE production. The project successfully accomplished the proposed target performance by producing mixed rare earth oxide (REO) with greater than 90% purity by weight in a continuous pilot scale operation from two distinctly different coarse refuse materials (i.e., West Kentucky No. 13 and Fire Clay coal seams), and at least three secondary sources (i.e., heap leach process and naturally formed acid mine drainage system). Project partners included the University of Kentucky, Virginia Tech, West Virginia University, Alliance Coal, Blackhawk Mining, Mineral Refining Company, and Mineral Separation Technologies. The pilot scale test facility was constructed at a former mining complex owned by Alliance Natural Resource Partners (Alliance Coal). The site was rehabilitated to accommodate the equipment installation, construction and fabrication, electrical power requirement, water line management and containment. The process units constructed and installed included X-ray sorting unit, crushing and grinding unit, physical separation unit, acid leaching unit, solvent extraction unit, and wastewater management unit. A rare earth mineral concentration unit was constructed as a standalone unit for flexible operation. A detailed environmental assessment and control plan was carried out to identify and quantify any potential impacts of the pilot-scale processing circuitry on the human and eco-system health and well-being. Corresponding mitigation strategies and control measures were provided. A conceptual flowsheet was developed to effectively remove thorium and uranium from high purity rare earth oxide mix or any potential radionuclide enriched stream. The two distinct feedstock materials were secured from the Blackhawk Mining Complex in eastern Kentucky where the Fire Clay (Hazard No. 4) seam is processed. The West Kentucky No. 13 (Baker) coarse refuse material was collected from an active process stream at an Alliance coal preparation plant located in western Kentucky. Characterization analysis indicated that both of feed materials generated from the two sources contained >300 ppm of TREEs on a dry whole mass basis which met the requirements for a qualified feed stock. The two feedstocks were further upgraded using a dual x-ray sorter to prepare the feed material for hydrometallurgical circuit. Thermal treatment on feed material prior to leaching was found to: 1) improve the leaching recovery of REEs, 2) increase the leaching kinetics, and 3) allow the leaching reaction to occur at lower acidity. Roasting at 600°C was selected as the pre-treatment condition for both West Kentucky No. 13 and Fire Clay coarse refuse material. Over 40% of leaching recovery was achieved by roasting West Kentucky No. 13 material having a top particle size of 3 mm in the pilot scale operation using 1.2M sulfuric acid leaching at 75OC. Initial pilot scale testing involved continuous operation of the pilot plant for 94 hours. The leaching unit was operated at solid-to-liquid ratio of 1 to 10 (w/v) using 0.5M sulfuric acid solution at a temperature of 75°C. The continuous solvent extraction circuit utilized rougher and cleaner units with DEHPA and TBP as the extractants. An innovative stripping circuit was developed to accumulate the REE concentration in the stripping solution to a level above 600 ppm. A bleed stream from the recycled strip solution was treated using oxalic acid precipitation which produced a high grade rare earth oxalate. The oxalate product was roasted to remove the oxalate which produced a rare earth oxide product having a purity greater 90%. Due to high concentrations of contaminant ions in the pregnant leach solution (PLS), a modified flowsheet was developed that involved pre-concentration of the REEs using multiple stages of precipitation and redissolution. The advantage of this process was improved removal of contamination before the downstream purification process and a significant cost reduction relative to the circuit that utilized the solvent extraction process. The modified circuitry included processes involving leaching, multistage precipitation, redissolution, and oxalate precipitation followed by roasting of the oxalate product. The circuit produced a mixed REO that was 92.96% pure from the initial test. A detailed parametric test plan was carried out which involved varying key parameters including solids feed rate, acid flowrate, acid concentration, multistage precipitation pH, redissolution pH, oxalate precipitation dosage and pH. The response variables included REE recovery, contaminant recovery, REO product grade and overall chemical consumption. Test results indicated that the acid-to-solid ratio is the key parameter to leaching efficiency as performance deteriorated with an increase in solids concentration. The optimal pH determined for REE precipitation and redissolution was 6.5 and 2.5, respectively. Additional tests were conducted to further improve the flowsheet. Recirculating a portion of the PLS to the feed of the leach tanks improved the leaching performance by lowering the pH of the leaching system and reducing the contamination recovery by shortening the residence time. Moreover, the removal of Al prior to REE precipitation significantly reduced the oxalic acid consumption in the oxalate precipitation circuit. The modified circuit produced over 90% grade REO by weight from both West Kentucky No. 13 and Fire Clay coarse refuse material in pilot scale continuous test programs. A case analysis model was developed to project the REE and major contaminants concentration in each PLS stream based on the leaching condition, pH cut point, and oxalic acid dosage. A correlation was established using empirical and semi-empirical models. Using the models, chemical consumption required for each stage was predicted based on the projected performance of the hydrometallurgy circuit. After identifying the optimum conditions, validation tests were carried out for the treatment of both West Kentucky No. 13 and Fire Clay coarse refuse materials in the pilot plant. The actual circuit performance and chemical consumptions were very close to the model predictions. Other than the two coarse refuse sources, several secondary feedstocks were also tested in the pilot plant facility. A “heap leach” system was constructed using the coarse refuse material generated from cleaning the West Kentucky No. 13 seam coal. Using the two stage SX rougher and cleaner circuit, a concentrate with a grade >90% REO was produced while recovering >97% of the REEs from the heap leach PLS. Naturally generated acid mine drainage (AMD) from West Kentucky No.13 mine was processed using the multistage precipitation circuit in the pilot plant in a test conducted for a period of 32 hours. The final grade of the mix RE oxide produced from the AMD was 90.84% with an overall circuit recovery of 64%. The primary source of REE was the selective precipitation steps involving iron and aluminum rejection. The hydrophobic-hydrophilic separation (HHS) process was proven to effectively recover coal from fine waste materials. For REM recovery, the HHS process was able to produce concentrates at grades of approximately 1.8% REE on an ash basis; however, recovery values were typically low, <10%, under the optimal conditions determined in the laboratory-scale testing. Staged testing of the pilot-scale HHS process for coal recovery and semi-continuous laboratory testing for REM testing showed that a total concentration ratio of more than 15x was observed for the REM recovery process. A circuit simulation package was developed for REE extraction and purification using a spreadsheet-based platform (Microsoft Excel). The REESim circuit simulation package is configured to track the mass and volume flows of components passing through a series of unit operations specified and configured by the user. The mass rates can then be utilized by the user to determine important performance indicators such as product mass yields, concentrate purity levels, element-by-element recoveries, and so forth. The techno-economic analysis showed that the roasting and leaching operations were the most expensive capital items, each contributing approximately 30% to the total capital cost. One notable contributor to the high production costs was the low REE recovery observed in the pilot scale trials. The product basket price was shown to have a strong influence on the economic viability of the scenarios, with the scandium price being the most significant influencer. Operating cost was shown to be extremely sensitive to REE recovery, REE feed grade, and leaching acid consumption. An analysis of ten different scenarios for a 500 t/h commercial operation revealed that three were economically favorable, producing internal rates of return varying from 27.7% to 33.1% and payback periods of 4 to 5 years. The project successfully developed and demonstrated a process to recover REEs from coal and coal byproducts in a pilot-plant operation which consistently produced over 90% grade REO mix from varies types of feedstocks. Commercialization analysis showed that the technology readiness level successfully achieved TRL 6 at the end of the project and demonstrated the need and the potential for scaling the process to further advance the technologies toward the goal of providing a domestic supply of REEs at a commercial scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

Development of Leaching Processes for the Recovery of Rare Earth Elements from Acid Mine Drainage Precipitates

Acid mine drainage (AMD) has been a challenge for mine operators to address and has had significant environmental impacts when there is a failure to address it. Fortunately, there is a regulation in the US that requires the treatment of AMD before water can be discharged into the environment. AMD is generated when sulfide minerals are exposed to water and air from mining. The acidic water then leaches metals from the surrounding rock, creating the potential for environmental contamination of this acidic water containing dissolved metals. AMD can contain high concentrations of metals like iron, aluminum, and manganese and also have been shown to contain trace concentrations of critical minerals, including rare earth elements (REEs). This environmental waste stream is now being researched as a potential source for REEs. There is a patented process for processing and extracting REEs from AMD which produces rare earth oxide preconcentrate (REOP) from AMD treatment precipitates and a final stage mixed rare earth oxide (MREO) product. This body of research examines a selective leaching process for each of these products and determines the activation energy associated with the leaching processes. Acid leaching with HCl was examined to selectively leach REEs from REOP while contaminant metals remained in the solid residue. The maximum leaching recovery of the REEs from the REOP was approximately 90% and an activation energy of 6.4 kJ/mol at pH 3.0. Ammonium chloride leaching was examined to selectively remove contaminant metals from a MREO product. The ammonium chloride process successfully leached major contaminant metals in excess of 85% recovery and had a maximum activation energy of 40.0 kJ/mol.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Dispersible Colloid Facilitated Release of Organic Carbon From Two Contrasting Riparian Sediments

In aqueous systems, including groundwater, nano-colloids (1–100 nm diameter) and small colloids (<450 nm diameter) provide a vast store of surfaces to which organic carbon (OC) can sorb, precluding its normal bioavailability. Because nanomaterials are ubiquitous and abundant throughout Earth systems, it is reasonable that they would play a significant role in biogeochemical cycles. As such, mineral nano-colloids (MNC) and small colloids, formed through mineral weathering and precipitation processes, are both an unaccounted-for reservoir and unquantified vector for transport of OC and nutrients and contaminants within watersheds. Water extractions and leaching experiments were conducted under (1) aerobic (ambient) and (2) anaerobic (environmental chamber) conditions for each of two contrasting riparian sediments from (1) Columbia River, Washington and (2) Tims Branch, South Carolina. Water dispersible colloid-adsorbed OC was as high as 48% of OC for Tims Branch anaerobic batch water extraction and as low as 0% for Columbia River aerobic batch water extractions. Anaerobic leaching from column experiments yielded higher colloid and OC release rates. Transmission electron microscopy with electron dispersive spectroscopy mapping revealed organic carbon associated with aggregations of nano-particulate silicate minerals and Mossbauer identified nano-particulate goethite. This exploratory study demonstrates that mineral facilitated release of OC in riparian sediments is both significant and variable between locations.

Rod, Kenton A.↗
DOE OSTI2023

Vadose Zone Soil Flushing for Chromium Remediation: A Laboratory Investigation to Support Field‐scale Application

Cr(VI) flushing from the vadose zone to the groundwater (with subsequent Cr(VI) removal in groundwater by pump-and-treat system) is a promising remedial technique that has recently been used at field scale. This laboratory study was conducted to provide the technical basis to design a field soil flushing strategy. The objectives were to (1) quantify the relationship between sediment Cr(VI) and Cr(III) mass and release rates and subsequent Cr(VI) leaching; (2) investigate different methodologies to maximize Cr(VI) leaching, and (3) investigate methods to minimize leaching of remaining residual Cr. Characterization of Cr-contaminated sediments (Hanford Site, WA) exhibited Cr(VI) showed that leach rates that were correlated to different Cr surface phases. Sediments with low leachable Cr(VI) (<2 μg/g) leached Cr rapidly, so slow infiltration of water in a single pulse was sufficient to leach most Cr. In contrast, sediments with high Cr (2 to 200 μg/g) released some Cr(VI) quickly but 10 to 50% Cr(VI) slowly (tens to hundreds of hours). Efficient unsaturated leaching of these sediments required a different infiltration strategy that includes: multiple slow leach pulses with time between flushing cycles; the use of a surfactant to increase Cr leaching from low-permeability zones, and the use of a reductant (Na-dithionite or Ca-polysulfide) in the final leach water was highly effective at decreasing residual Cr leaching. This study clearly demonstrated that the methodology of basing laboratory Cr flushing on parameters such as Cr release mass and rates could be used to improve the efficiency of soil flushing at field scale.

Accelerated Cr Flushing↗
DOE OSTI2020

SiC compatibility

SiC is a relatively chemically stable ceramic that has potential use in the extreme environments present in nuclear reactors. Reactions with high temperature steam, He, hydrothermal, molten salts, and liquid metals are some of the possible environments that SiC could be exposed to. While it is very stable in air, aqueous environments and very low oxygen partial pressures can lead to SiC recession. Generally, SiC does not react with the FliNaK or FliBe molten salts, or liquid metals, however contaminants in these working fluids leached from other materials can cause reaction layers to occur. Most of these systems require additional testing under neutron irradiation to determine if there are any combined effects.

Mouche, Peter↗
DOE OSTI2022

Polydiketoenamines for a Circular Plastics Economy

The mismanagement and leakage of plastic waste into the environment are failures of modern society. Once in the environment, plastic waste degrades into microplastics on a time scale dependent on the resin chemistry and the associated biotic or abiotic process. Here, the high surface area of microplastics results in the contamination of ecosystems through the leaching of toxic chemicals compounded with plastics during manufacturing. In addition, the small size of microplastics increases the likelihood that they will be inhaled or ingested, which has led to the bioaccumulation of microplastics with documented harm. Furthermore, microplastics are more readily aerosolized and distributed by weather systems to areas remote from locations where plastic waste has been mismanaged. Consequently, the carbon cycle must now account for plastic waste discharge, degradation, and dispersal in the environment after the end of useful life on a global scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL Radiological Response Training Range

This assessment uses screening-level models to calculate potential environmental impacts from proposed tests at the Idaho National Laboratory (INL) Radiological Response Training Range (RRTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K2O, LaBr3, KBr, Cu, Zr, F, Ga, Ga2O3, NaNO2, Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface-soil impacts were calculated with the computer program mixing-cell model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated assuming 12 tests are conducted annually using all 11 material types for a period of 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer-code input, output, executable files, batch files, scripts, and spreadsheet files are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS). It is highly unlikely the test scenarios evaluated in this ECAR will adversely impact human health based on comparisons of calculated dose and concentration against regulatory standards and risk-based screening levels. Conservative estimates of dose to workers and the public from atmospheric transport of possible radionuclide releases are far below federal radiation protection standards. Conservative estimates of potential contaminant concentrations in groundwater are less than federal drinking water standards or screening levels. Predicted radionuclide concentrations in surface soils are below risk-based screening levels, except for Ge-68 (material Ga-68) for the worker. The Ge-68 soil concentration can be made less than the worker PRG, if the number of annual tests using Ga-68 is reduced from 12 to 6. However, the sum of ratios still exceeds one because of the high K-40 ratio. If the EF of the worker (number of days the worker is in the contaminated testing area) is reduced from 225 days/yr (default value for full time worker) to 112 days/yr, the Ge-68 ratio is less than one and the sum of ratios is less than one. Actual radiation doses and groundwater and surface-soil concentrations are likely to be much less than those calculated because of the conservative assumptions and parameters employed in the modeling. For example, atmospheric-transport calculations assume the entire inventory of each material type is readily released to the atmosphere and no plume deposition, depletion, or radioactive decay occurs during transport. The calculations also assume the same meteorological conditions (e.g., wind velocity, wind direction, stability class) that produce the maximum 95th percentile concentration (i.e., concentration representing the 95th percentile of a distribution of concentrations derived from 3 years of hourly meteorological data) at each receptor location are the same for all 12 tests during the year, and each receptor is assumed to be present during all 12 tests. The surface-soil assessment assumes the entire inventory of each test is deposited in the top 5 cm of soil. No atmospheric dispersal is assumed, and the radionuclides are subject only to leaching and radioactive decay. The groundwater-pathway modeling is conservative in that it is one-dimensional in the unsaturated zone (no lateral spreading/dilution) and assumes the entire inventory of contaminants infiltrates into the ground at the same location for every test. This is especially conservative for particulate radionuclides because they would have to dissolve or corrode first and some would be dispersed into the atmosphere. The groundwater receptor is also assumed to consume water directly from a hypothetical well positioned in the location of maximum concentration. In addition, conservative degradation rates were used, and volatilization was not considered for the nonradioactive chemical

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL National Security Test Range

This assessment uses screening-level models to calculate potential environmental impacts from proposed tests at two locations at the Idaho National Laboratory (INL) National Security Test Range (NSTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K 2 O, LaBr 3 , KBr, Cu, Zr, F, Ga, Ga 2 O 3 , NaNO 2 , Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface-soil impacts were calculated with the computer program mixing-cell model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated based on the assumption that 12 tests are conducted annually using all 11 material types for 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer-code input, output, executable files, batch files, scripts, and spreadsheet files, are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS). It is highly unlikely the test scenarios evaluated in this ECAR will adversely impact human health based on comparisons of calculated dose and concentration against regulatory standards and risk-based screening levels. Conservative estimates of dose to workers and the public from atmospheric transport of possible radionuclide releases are far below federal radiation protection standards. Conservative estimates of potential contaminant concentrations in groundwater are less than federal drinking water standards or screening levels. Predicted radionuclide concentrations in surface soils are below risk-based screening levels, except for Ge-68 (material Ga-68) for the worker. The Ge-68 soil concentration can be made less than the worker PRG, if the number of annual tests using Ga-68 is reduced from 12 to 6. However, the sum of ratios still exceeds one because of the high K-40 ratio. If the EF of the worker (number of days the worker is in the contaminated testing area) is reduced from 225 days/yr (default value for full time worker) to 112 days/yr, the Ge-68 ratio is less than one and the sum of ratios is less than one. Actual radiation doses and groundwater and surface-soil concentrations are likely to be much less than those calculated because of the conservative assumptions and parameters employed in the modeling. For example, atmospheric-transport calculations assume the entire inventory of each material type is readily released to the atmosphere and no plume deposition, depletion, or radioactive decay occurs during transport. The calculations also assume the same meteorological conditions (e.g., wind velocity, wind direction, stability class) that produce the maximum 95th percentile concentration (i.e., concentration representing the 95th percentile of a distribution of concentrations derived from 3 years of hourly meteorological data) at each receptor location are the same for all 12 tests during the year, and each receptor is assumed to be present during all 12 tests. The surface-soil assessment assumes the entire inventory of each test is deposited in the top 5 cm of soil. No atmospheric dispersal is assumed, and the radionuclides are subject only to leaching and radioactive decay. The groundwater-pathway modeling is conservative in that it is one-dimensional in the unsaturated zone (no lateral spreading/dilution) and assumes the entire inventory of contaminants infiltrates into the ground at the same location for every test. This is especially conservative for particulate radionuclides because they would have to dissolve or corrode first and some would be dispersed into the atmosphere. The groundwater receptor is also assumed to consume water directly from a hypothetical well positioned in the location of maximum concentration. In addition, conservative degradation rates were used, and volatilization was not considered for the nonradradioactive chemicals modeled. And finally, the calculations assume all 12 tests will be performed at the same place at both locations, and all 11 radioactive material types will be used for each test. This is conservative because it is anticipated that no more than two material types will be used per test.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2021

Arsenic hyperaccumulator Pteris vittata shows reduced biomass in soils with high arsenic and low nutrient availability, leading to increased arsenic leaching from soil

Plant-soil interactions affect arsenic and nutrient availability in arsenic-contaminated soils, with implications for arsenic uptake and tolerance in plants, and leaching from soil. In 22-week column experiments, we grew the arsenic hyperaccumulating fern Pteris vittata in a coarse- and a medium-textured soil to determine the effects of phosphorus fertilization and mycorrhizal fungi inoculation on P. vittata arsenic uptake and arsenic leaching. We investigated soil arsenic speciation using synchrotron-based spectromicroscopy. Greater soil arsenic availability and lower nutrient content in the coarse-textured soil were associated with greater fern arsenic uptake, lower biomass (apparently a metabolic cost of tolerance), and arsenic leaching from soil, due to lower transpiration. P. vittata hyperaccumulated arsenic from coarse- but not medium-textured soil. Mass of plant-accumulated arsenic was 1.2 to 2.4 times greater, but aboveground biomass was 74% smaller, in ferns growing in coarse-textured soil. In the presence of ferns, mean arsenic loss by leaching was 195% greater from coarse- compared to the medium-textured soil, and lower across both soils compared to the absence of ferns. In the medium-textured soil arsenic concentrations in leachate were higher in the presence of ferns. Fern arsenic uptake was always greater than loss by leaching. Most arsenic (>66%) accumulated in P. vittata appeared of rhizosphere origin. In the medium-textured soil with more clay and higher nutrient content, successful iron scavenging increased arsenic release from soil for leaching, but transpiration curtailed leaching.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Water reactive polyurethane grouting for deep vadose zone contaminant immobilization

Contaminants in the deep vadose zone (DVZ) pose a long-term threat to groundwater, human health, and the environment. Polyurethane grouting is a type of chemical grouting that is potentially advantageous in immobilizing contaminants in DVZs. Polyurethane resin has low viscosity that makes it feasible to penetrate and fill the pore space between fine particles. Here, in this study a series of laboratory pressure grouting and leaching tests were conducted to simulate and assess the effectiveness of polyurethane grouting for immobilizing contaminants in DVZs. Soil with fine particles was prepared with 127 I (as iodide) that served as a non-radioactive surrogate for radioactive 129 I. After grouting and curing, leaching tests were used to measure and compare contaminant diffusivity and leachability index values. Additionally, changes in porosity and saturated hydraulic conductivity of grouted soil were measured. X-Ray Computer Tomography (XCT) results showed that the cured polyurethane was distributed nearly homogeneously and approximately half of the voids were filled with cured polyurethane. Grouting reduced the saturated hydraulic conductivity of soil by 37 %. The effective diffusivity decreased by more than 80 % as compared with the ungrouted soil. The leachability index of the grouted soil was 6.5; meeting the criteria established by the U.S. Nuclear Regulatory Commission (NRC) standard. The results obtained in this study provide a valuable assessment of polyurethane grouting for iodide immobilization in the DVZ and indicate this approach may be a viable method for contaminant remediation in DVZ soils.

Contaminant Diffusion↗
DOE OSTI2021

Evaluation of engineered sorbents for the sorption of mercury from contaminated bank soils: a column study

Abstract As a global environmental pollutant, mercury (Hg) threatens our water resources and presents a substantial risk to human health. The rate and extent of immobilization of Hg 2+ (hereafter, Hg) on engineered sorbents (Thiol-SAMMS®, pine biochar, SediMite™, Organoclay™ PM-199, and quartz sand as a control) was evaluated using flow-through column experiments. The effectiveness of the sorbents was based on (1) the percentage of Hg removed in relation to the total amount of Hg passing the sorbent column, and (2) the rate of Hg uptake compared to the nonreactive tracer bromide (Br − ). All sorbents removed Hg to a certain extent, but none of the sorbents removed all the Hg introduced to the columns. Thiol-SAMMS showed the highest mean percentage of Hg removed (87% ± 2.9%), followed by Organoclay PM-199 (71% ± 0.4%), pine biochar (57% ± 22.3%), SediMite (61% ± 0.8%), and the control quartz sand (11% ± 5.6%). Thiol-SAMMS was the only sorbent to exhibit retardation of Hg in comparison to the conservative tracer Br − . For the remaining sorbents, Br − along with low concentrations of Hg were eluted within the first 3 pore volumes, indicating limited retardation of Hg. Overall, removal of Hg by sorbents was substantial, suggesting that sorbents might be suitable for deployment in contaminated environments. High concentrations of DOM leaching from the soil columns likely influenced the speciation of Hg and inhibited sorption to the sorbents. Incomplete removal of Hg by any sorbent suggests that additional optimization is needed to increase efficiency.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL Radiological Response Training Range

This assessment uses screening level models to calculate potential environmental impacts from proposed tests at the Idaho National Laboratory (INL) Radiological Response Training Range (RRTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K 2 O, LaBr 3 , KBr, Cu, Zr, F, Ga, Ga 2 O 3 , NaNO 2 , Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface-soil impacts were calculated with the computer program Mixing-Cell Model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated based on the assumption that 12 tests are conducted annually using all 11 material types for a period of 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer code input, output, executable files, batch files, scripts, and spreadsheet files are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2024

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL National Security Test Range

This assessment uses screening level models to calculate potential environmental impacts from proposed tests at two locations at the Idaho National Laboratory (INL) National Security Test Range (NSTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K 2 O, LaBr 3 , KBr, Cu, Zr, F, Ga, Ga 2 O 3 , NaNO 2 , Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface soil impacts were calculated with the computer program Mixing-Cell Model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated based on the assumption that 12 tests are conducted annually using all 11 material types for 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer code input, output, executable files, batch files, scripts, and spreadsheet files, are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2023

Rapid denitrification of nitrate-contaminated groundwater in a low-gradient blackwater stream valley

Leaching of excess nitrogen (N) to groundwater in fertilized landscapes can overwhelm natural biogeochemical processes and cause long-term eutrophication of aquatic systems. We investigated N fate and transport from an intensively managed short-rotation woody crop (Pinus taeda) plantation through the riparian zone of an intermittent, low-gradient blackwater stream. Fertilization of the P. taeda plantation on the uplands resulted in contamination of groundwater with nitrate concentrations between 0.9 and 1.9 mg N L -1 . No corresponding increase in nitrate was observed in stream water or shallow groundwater in the riparian zone. Groundwater travel-time modeling predicted that N from near-stream, upland plantation areas should have reached streams during the monitoring period. Two years of measuring N species in well water in contrasting landscape positions (within the plantation, swale, riparian edge, forested hillslope, and valley), indicated rapid nitrate transformation and denitrification within the forested wetland valleys. Denitrification in the shallow groundwater system within the toeslopes and the riparian zone was estimated to have removed > 90% of nitrate. Finally, these results highlight the importance of riparian zones as pathways for the removal of N and for controlling downstream N loads.

54 ENVIRONMENTAL SCIENCES↗
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.↗
DOE OSTI2021

Application of Eh-pH Diagrams on Acid Leaching Systems for the Recovery of REEs from Bastnaesite, Monazite and Xenotime

Bastnaesite, monazite and xenotime are rare earth minerals (REMs) that are typical sources for rare earth elements (REEs). To advance the understanding of their leaching and precipitation behavior in different hydrometallurgical processes, Eh-pH diagrams were constructed and modified using the HSC 9.9 software. The aqueous stability of rare earth elements in H 2 O and acid leaching systems, i.e., the REE-Ligands-H 2 O systems, were depicted and studied based on the Eh-pH diagrams. This study considers the most relevant lixiviants, their resulting equilibrium states and the importance in the hydrometallurgical recovery of rare earth elements (REMs). A literature review was performed summarizing relevant Eh-pH diagrams and associated thermodynamic data. Shifting stability regions for REEs were discovered with additions of acid ligands and a narrow stability region for soluble REE-(SO 4 /Cl/NO 3 ) complexes under highly acidic conditions. As such, the recovery of REEs can be enhanced by adjusting pH and Eh values. In addition, the Eh-pH diagrams of the major contaminants (i.e., Fe, Ca and Al) in leaching systems were studied. The resulting Eh-pH diagrams provide possible insights into potential passivation on the particle surfaces due to the formation of an insoluble product layer.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Parametric study and speciation analysis of rare earth precipitation using oxalic acid in a chloride solution system

Oxalic acid precipitation is a common step in the purification of rare earth elements (REE) from a concentrated pregnant leach solution (PLS). However, the presence of contaminants such as Al, Fe, and Ca in given amounts decreases the REE precipitation efficiency and product purity while also increasing the amount of oxalic acid needed to maximize recovery. As such, a statistically designed test program was performed to identify the optimal conditions necessary for a relatively low REE content PLS containing elevated concentrations of contaminant ions. The performance objective was maximization of REE precipitation efficiency while minimizing the oxalic acid dosage. A central composite design was utilized to quantify performance impacts and identify the ultimate set of parameter values for oxalic acid dosage, Fe(III) contamination concentration, solution pH, and reaction temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicate that increasing the oxalic acid concentration from 0 g/L to 80 g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. Here, to further the understanding of the REE-oxalate system, a fundamental solution chemistry study was performed using the equilibrium constants of the reactions. The study resulted in the development of oxalate speciation diagrams and provided an analysis of the REE precipitation characteristics at various oxalate anion concentrations and Fe(III) contamination levels using MINTEQ software. The dominant Fe(III) species in the solution system were found to be Fe-(C 2 O 4 ) 3 3- , Fe-(C 2 O 4 ) 2- , and Fe-(C 2 O 4 ) + , which consume the majority of the oxalate anions. The simulated model was found to be in agreement with the experimental findings and helped to explain the adverse impact of increased iron concentrations on REE precipitation efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗