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DOE OSTI2024

FIU Project 2: Environmental Remediation Science & Technology [Slides]

FIU’s research under this project involves conducting basic and applied science to fill knowledge gaps and validate potential remediation technologies for contaminated soil and groundwater and the assessment of the fate and transport of contaminants in the environment. The aim of FIU’s research is to reduce the potential for contaminant mobility or toxicity in the surface and subsurface through the development and application of state-of-the-art scientific and environmental remediation technologies at the Hanford Site, Savannah River Site (SRS), and the Waste Isolation Pilot Plant (WIPP), which is the Nation’s only mined geologic repository for permanent disposal of transuranic waste. FIU collaborates with scientists from Pacific Northwest National Laboratory (PNNL), Savannah River National Laboratory (SRNL), Savannah River Ecology Laboratory (SREL), Los Alamos National Laboratory (LANL) and the DOE Carlsbad Field Office (CBFO) in order to plan and execute research that is synergistic with the work being conducted at the sites, and that supports the resolution of critical science and engineering needs which leads to a better understanding of the long-term behavior of subsurface contaminants. The knowledge gained through this research will be used to transform experimental and modeling innovations into practical applications deployed at the sites to support EM’s primary goal of expediting the closure of major contaminated soil and groundwater sites and waste units. Collaborative relationships between FIU and the national laboratories have provided large benefits over the years to FIU, the national laboratories, the DOE complex, and the DOE EM mission. By working closely with the national laboratories, FIU’s research is not only closely aligned with the cleanup mission priorities at the DOE sites, but complements and supports ongoing work at the national laboratories for screening of new remedial technologies. This coordination and leveraging of research efforts results in time- and cost-savings, and will accelerate progress of the DOE EM environmental restoration mission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2023

Sewage Treatment Plant #1 Area, SWMU 117 Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment Progress Report

This Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment (SA) Progress Report (SAPR) discusses the investigation activities and findings for the Sewage Treatment Plant #1 (STP1) Area located at Kennedy Space Center (KSC), Florida (Figure 1-1). This site has been designated Solid Waste Management Unit (SWMU) 117 under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program, as the sewage treatment plant and associated areas were identified as a potential source of PFAS to the environment. This PFAS SAPR was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under Indefinite Delivery Indefinite Quantity Contract 80KSC019D0011-80KSC019F0070. This is the first progress report to document on-going SA activities; supplemental progress reports will be provided as additional data is collected. PFAS SA activities were conducted between April 2020 and March 2022 to collect additional data to supplement the existing datasets to better understand the extent of PFAS impacts to the environment in the STP1 Area. The SA for the STP1 Area covers an approximately 130-acre investigation area with multiple structures and buildings. The focus of the SA is the STP1 Complex and associated structures, including the former Polishing Pond, former Sludge Disposal8 Area, and former Spray Field. The STP1 Complex is located in the KSC Industrial Area, at the southwest corner of 4th Street SE and C Avenue SE. The STP1 Complex is located approximately ¼-mile south and downgradient of the Fire Station #1 site (SWMU 116), which is also currently undergoing a PFAS SA because of potential releases of PFAS-containing aqueous film-forming foam (AFFF). During the SA, a total of seven soil, 131 groundwater direct push technology (DPT), 24 groundwater monitoring well, and 11 surface water samples were collected between April 2020 and March 2022. Monitoring well samples were analyzed for 18 PFAS compounds, with all other samples analyzed for 28 PFAS compounds. The SA sample results were used along with historical results to evaluate the extent of PFAS impacts to the environment in the STP1 Area. Data generated to date and prior results were screened against the United States Environmental Protection Agency (USEPA) May 2022 Tap Water Regional Screening Levels (RSL) for groundwater and residential RSLs for soil (hazard quotient of 0.1). Surface water results were screened against the State of Florida Human Health Surface Water Screening Levels (SWSLs). Results from the SA showed exceedances of the applicable screening criteria for groundwater and surface water. Considering the current and historical dataset, PFOS is the prevalent PFAS compound. Based on these results, additional groundwater DPT and surface water sampling should be considered for PFAS analysis, focused on evaluating surface water bodies in the southeast portion of the Industrial Area, which discharge into the Banana River. Additionally, installation of monitoring wells should be considered to evaluate the interaction between the groundwater and surface water at the site. Collection of additional samples for TOC analysis should also be considered from representative groundwater (saturated soils) and surface water locations to further evaluate potential correlations between PFAS and TOC to provide a more comprehensive dataset to assist in fate and transport analyses.

Sewage Treatment Plant↗

DOE OSTI2022

Riverine Plastic Pollution: Sampling and Analysis Methods

Riverine plastic pollution has been found in all major U.S. rivers, but the exact amount of plastic being released to the oceans has not been quantified. Field studies conducted in U.S. rivers have used a range of sampling and analysis techniques and rarely measured the mass of the plastic collected. Measurements of riverine plastic pollution are needed to calibrate and validate models used to estimate the U.S. riverine plastic emissions to the oceans. This report surveys measurement methods used to quantify riverine pollution and current estimates of U.S. riverine plastic pollution from measurements and models. Measurement methods include field sampling and laboratory analysis. Field sampling methods are described for large (macro) and small (micro) plastic particles. Laboratory analysis methods are described for macro and microplastic with an emphasis on the detailed characterization processes of microplastics. Waterborne leachate analysis is also briefly described. Three models are described that estimate plastic pollution based on mismanaged plastic waste in the river catchment basins. The models were validated and calibrated with global data sources. The data sources were predominantly outside of the U.S., where the magnitude and composition of plastic pollution is different than what is found in U.S. rivers. Comprehensive measurements of riverine plastics are needed not only to characterize the riverine plastic pollution, but also parameterize and validate models of plastic fate and transport. This report also describes five key U.S. rivers that span a range of sizes and environmental conditions that could be sampled to obtain data to support characterization and model development of plastic pollution from rivers to oceans. Sampling and analysis protocol recommendations are made to ensure the highest quality of data are collected in the five rivers.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Development of Cr, Se, U, Sb, and Te isotopes as indicators of redox reactions, contaminant fate, and contaminant transport in aqueous systems: A review

Cr, Se, U, Sb, and Te are toxic, redox-active elements that are more mobile and environmentally problematic in their oxidized forms, and less mobile and bioavailable in their reduced forms. This chapter reviews the development of Cr, Se, U, Sb, and Te isotope ratio measurements as new indicators of redox reactions and contaminant migration. Reliable analytical methods exist, but are still evolving. Understanding of isotopic fractionation induced by various (bio)geochemical processes has been explored in dozens of publications, yet is far from complete: Reduction reactions, the major driver of isotopic variation, have been relatively well studied. However, the magnitude of fractionation is variable and the systematics of that variation are still being explored. Isotopic fractionation induced by oxidation reactions is not well understood. Non-redox reactions, which involve smaller changes in bonding of these elements, tend to induce less isotopic fractionation, but can nonetheless cause significant isotopic shifts. Field applications of Cr, Se, U isotope ratios have demonstrated that they are useful as indicators of reduction in natural systems. A few studies suggest they are also useful as indicators of oxidation and contaminant sources. The physical and chemical complexity of groundwater systems hinders accurate quantitative interpretation of Cr, Se, U isotope data using simple models. Numerical models have been developed that capture the behavior of complex, coupled systems and enable the most effective extraction of information from field data sets.

58 GEOSCIENCES↗

DOE OSTI2024

Comprehensive Cradle to Grave Life Cycle Analysis of On-Road Vehicles in the United States based on GREET

To properly compare and contrast the environmental performance of one vehicle technology against another, it is necessary to consider their production, operation, and end-of-life fates. Since 1995, Argonne’s GREET® life cycle analysis model (Greenhouse gases, Regulated Emissions, and Energy use in Technologies) has been annually updated to model and refine the latest developments in fuels and materials production, as well as vehicle operational and composition characteristics. Updated cradle-to-grave life cycle analysis results from the model’s latest release are described for a wide variety of fuel and powertrain options for U.S. light-duty and medium/heavy-duty vehicles. Light-duty vehicles include a passenger car, sports utility vehicle (SUV), and pick-up truck, while medium/heavy-duty vehicles include a Class 6 pickup-and-delivery truck, Class 8 day-cab (regional) truck, and Class 8 sleeper-cab (long-haul) truck. Powertrain coverage includes internal combustion (spark ignition and compression ignition) engines, hybrid electric, plug-in hybrid, full battery electric, and fuel cell vehicles powered by conventional and low carbon energy sources. The results offer insights into the current state of these technologies, as well as a projection of the likely environmental implications of future fuel and vehicle advancements through a time-series evaluation of life cycle greenhouse gas emissions.

Kelly, Jarod C.↗

DOE OSTI2020

CO 2 plume evolution in a depleted natural gas reservoir: Modeling of conformance uncertainty reduction over time

Uncertainty in the long-term fate of CO 2 injected for geologic carbon sequestration (GCS) is a significant barrier to the adoption of GCS as a greenhouse-gas emission-mitigation for industry and regulatory agencies alike. Here, we present a modeling study that demonstrates that the uncertainty in forecasts of GCS site performance decreases over time as monitoring data are used to update operational models. We consider a case study of GCS in a depleted natural gas reservoir, with CO 2 injection occurring over 20 years, with a 50-year post-injection site care period. We constructed a detailed model to generate the actual model output, which is considered synthetic observation data. A series of simpler operational models based on limited data and assumptions about how an operator would model such a site are then run and compared against actual model output at specific monitoring points after one year, two years, etc. The operational model is updated and improved using the synthetic observation data from the actual model at the same time intervals. Model parameter values and model features needed to be updated over time to improve matches to the actual model. These kinds of model adjustments would be a normal part of reservoir engineering and site management at GCS sites. Uncertainty in two key measures related to site performance decreases with time: extent of the CO 2 plume up-dip migration, and radial extent of the pressure pulse. This conclusion should help allay the concerns of industry and regulators about uncertainty in long-term fate of CO 2 at GCS sites.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Carbon Mineralization of Sulfate Wastes Containing Pb: Synchrotron Pb M3-Edge XANES Analysis of Simultaneous Heavy Metal and Carbon Sequestration

Sulfate wastes are produced in large quantities and contain toxic heavy metals such as lead (Pb), posing environmental risks. Because of favorable solubility differences, these wastes can be repurposed for engineered carbon dioxide (CO 2 ) sequestration. Understanding the fate and mobility of heavy metals during this process is important. This study focuses on Pb and the effect of zinc (Zn) on Pb in carbon mineralization. Synthesized gypsum was treated with a carbonate-rich solution at pH 11.5 to convert the sulfates to carbonates. Aqueous solutions and mineral solids were analyzed. Synchrotron-based micro-X-ray fluorescence and a novel application of Pb M3-edge X-ray absorption near-edge structure provided detailed insights into Pb distribution and mineral forms. Results showed significant reductions in aqueous Pb and Zn concentrations, indicating effective metal sequestration. Carbon mineralization transformed Pb from soluble anglesite (PbSO 4 ) into insoluble cerussite (PbCO 3 ) and hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2 ). Pb primarily precipitated onto calcium carbonate surfaces through surface-mediated precipitation reactions. While the presence of Zn modified crystallization dynamics, it did not impede Pb sequestration and potentially enhanced surface reactivity, facilitating greater Pb immobilization. These findings highlight carbon mineralization as a sustainable approach to immobilize toxic metals in sulfate wastes while advancing CO 2 sequestration efforts.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Acetonitrile Destruction and Fate of Organics in the Reverse Osmosis System at the ETF

The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams that include condensates from the 242-A evaporator, leachate from the Environmental Restoration Disposal Facility (ERDF), as well as laboratory wastes and, in the future, will treat liquid effluents from the Hanford Tank Waste Treatment and Immobilization Plant (WTP) and Integrated Disposal Facility (IDF) leachate. Liquid effluents from the WTP will have significant concentrations of acetonitrile. Acetonitrile is formed by reaction of nitrates and sugar in the WTP low activity waste (LAW) melters and is prevalent in the submerged bed scrubber (SBS) and wet electrostatic precipitator (WESP) liquid effluents from WTP off-gas treatment. When these liquids are concentrated in the WTP Effluent Management Facility (EMF) evaporator in the direct feed low activity waste (DFLAW) flow-sheet, testing has shown that the majority of the acetonitrile partitions to the evaporator condensate. Since the evaporator condensate is directed to the ETF, this creates a potential issue with the ETF waste acceptance criteria. Consequently, there is a need to validate flow-sheet assumptions on the fate of acetonitrile and other organics within the ETF. The present plan includes the addition of a steam stripper to the ETF to remove acetonitrile. There is, therefore, also a need to determine a suitable method to destroy acetonitrile in the overhead condensate stream from the new steam stripper. Washington River Protection Solutions, LLC (WRPS) previously contracted with Atkins and the Vitreous State Laboratory (VSL) of The Catholic University of America (CUA) to perform development and testing work to evaluate potential methods for destruction of acetonitrile in WTP secondary liquid effluents. Based on the results of that work, WRPS requested that follow-on testing be conducted to further evaluate acetonitrile destruction in the steam stripper condensate using ultraviolet oxidation (UV/OX) with persulfate. WRPS also requested testing to assess the rejection rate of organics in the reverse osmosis (RO) system installed in the ETF. This report presents the results from testing to address those needs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Structure–reactivity relationships in the removal efficiency of catechol and hydroquinone by structurally diverse Mn-oxides

Catechol and hydroquinone are widely present hydroxybenzene isomers in the natural environment that induce environmental toxicities. These hydroxybenzene compounds can be effectively removed by manganese (Mn)-oxides via sorption and oxidative degradation processes. In the present study, we investigated the structure–reactivity relationships in the sorption and oxidation of catechol and hydroquinone on Mn-oxide surfaces. Two widely present Mn-oxides, including hydrous Mn oxide (HMO) and cryptomelane, comprised of layer and tunnel structures, respectively, are specifically studied. Effects of Mn-oxide structures and environmental pH conditions on the removal efficiency of these hydroxybenzene compounds, via sorption and oxidative degradation, are investigated. Cryptomelane, which has a higher specific surface area than HMO, possesses a higher sorption and oxidation capacity. The complexation mechanisms of catechol and hydroquinone vary due to their structure-induced difference in reactivity. Catechol reduced and dissolved more Mn from Mn-oxides than hydroquinone, accompanied by a higher C loss of catechol-C, suggesting a higher reactivity of catechol. Structural changes occurred in the Mn-oxides resulting from reaction with catechol and hydroquinone: reduction of Mn(IV), corresponding formation of Mn(III) and Mn(II) in the mineral, and free Mn 2+ ions released into the suspension. Finally, these insights could help us better understand and predict the fate of hydroxybenzene compounds in Mn-oxide-rich soils and wastewater treatment systems that generate Mn-oxides via Mn removal and the associated environmental toxicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Assessing horizontal gene transfer in the rhizosphere of Brachypodium distachyon using fabricated ecosystems (EcoFABs)

ABSTRACT Horizontal gene transfer (HGT) is a major process by which genes are transferred between microbes in the rhizosphere. However, examining HGT remains challenging due to the complexity of mimicking conditions within the rhizosphere. Fabricated ecosystems (EcoFABs) have been used to investigate several complex processes in plant-associated environments. Here we show that EcoFABs are efficient tools to examine and measure HGT frequency in the rhizosphere. We provide the first demonstration of gene transfer via a triparental conjugation system in the Brachypodium distachyon rhizosphere in an EcoFAB using Pseudomonas putida KT2440 as both donor and recipient bacterial strain with the donor containing a mobilizable and non-self-transmissible plasmid. We observed that the frequency of plasmid transfer in the rhizosphere is potentially dependent on the plant developmental stage and the composition and amount of root exudates. The frequency of plasmid transfer also increased with higher numbers of donor cells. We demonstrate the transfer of plasmid from P. putida to another B. distachyon root colonizer, Burkholderia sp. OAS925, showing HGT within a rhizosphere microbial community. Environmental stresses also influenced the rate and efficiency of HGT in the rhizosphere between different species and genera. This study provides a robust workflow to evaluate transfer of engineered plasmids in the rhizosphere when such plasmids are potentially introduced in a field or other plant-associated environments. IMPORTANCE We report the use of EcoFABs to investigate the HGT process in a rhizosphere environment. It highlights the potential of EcoFABs in recapitulating the dynamic rhizosphere conditions as well as their versatility in studying plant-microbe interactions. This study also emphasizes the importance of studying the parameters impacting the HGT frequency. Several factors such as plant developmental stages, nutrient conditions, number of donor cells, and environmental stresses influence gene transfer within the rhizosphere microbial community. This study paves the way for future investigations into understanding the fate and movement of engineered plasmids in a field environment.

Priya, Shweta↗

DOE OSTI2020

Mapping the Concentration Distribution of Contaminant Plumes to the Computational Grid of the Plateau to River Model (Ver. 8.3)

This environmental calculation file (ECF) outlines the process conducted for defining the initial condition groundwater plumes for select contaminants of interest (COIs) to the Plateau River model version 8.3 (P2Rv8.3) domain (CP-57037, Model Package Report: Plateau to River Groundwater Model Version 8.3). Various data sources were combined into a single set of files defining plume conditions at time 1/1/2018. The resulting files are intended for use as inputs for transport modeling to support forecasts of the Central Plateau contaminant plume fate and transport.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Chloroplast Stress Signals: Control of Retrograde Signaling, Chloroplast Turn-Over, and Cell Fate Decisions

Chloroplasts (photosynthetic plastids) are semiautonomous organelles that contain their own small genomes. The proteomes of chloroplasts, however, are a mixture of plastid and nuclear-encoded proteins. Chloroplasts perform photosynthesis, which is prone to damaging the organelles, leading to the production of reactive oxygen species (ROS) that damage the cell under environmental stresses. Thus, for the cell to maintain proper chloroplast function, efficient photosynthesis, and avoid ROS damage, it relies on complex crosstalk between the chloroplast, the nucleus, other organelles within the cell, and the cytoplasm in between. This communication involves retrograde signals from chloroplasts to control nuclear gene expression, programmed cell death (PCD), and chloroplast degradation. Here we review these signals with an emphasis on the roles of the ROS singlet oxygen ( 1 O 2 ) and plastid gene expression. We cover (1) recent work on understanding how multiple 1 O 2 signaling pathways can be initiated within stressed chloroplasts, (2) how individualized post-translational regulatory systems allow chloroplasts to control their proteomes and degradation, and (3) how chloroplast signals ultimately control cell fate decisions, such as PCD, senescence, and vacuole-mediated degradation of chloroplasts (chloroplast quality control). Overall, this chapter discusses how chloroplasts can act as environmental sensors for the cell and allow plants to acclimate to stress and thrive in dynamic environments.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2002

Noachian Martian Volcanics a Water Source

H2O was supplied to the Noachian atmosphere by eruptions, or in association with large impacts. Most water outgassed into an extremely cold atmosphere, and condensate deposits were inevitable. High heat flow could lead to subglacial melting only if ice thicknesses were greater than 500-1000m, which is extremely unlikely. Subareal melting and flow is contingent upon temperatures periodically exceeding 273 K, and retarding evaporative loss of the flow. In still air, evaporation into a dry atmosphere is in the free convection regime, and a stream with 2 cu m/s discharge, flowing 1 m/s could persist for hundreds of days and cover distances greater than any valley reach. The zero-wind-shear condition is considered implausible however. We investigate the possibility that evaporation rates were suppressed because the atmosphere was regionally charged with H2O as it moved over snow/ice fields. Our initial concern is precipitation from volcanic plumes. A Kilauea-style eruption on the martian surface would cover a 10km circular deposit with 10cm of H2O, if all H2O could be precipitated near the vent. The characteristics of the eruption at the vent, (vent size, temperature, H2O content, etc.) are independent of the environmental conditions. The subsequent behavior of the plume, including precipitation of ash and H2O condensate depends strongly on the environment. Hence, the proximal fate of volcanic H2O is amenable to treatment in a model. A simple bulk thermodynamic model of the rise of an H2O plume through a stably stratified CO2 atmosphere, with only adiabatic cooling, produces runaway plume rise. A more complex treatment includes the effects of latent heat release, wind shear along the plume, divergence of ash and H2O, and will yield more realistic estimates of H2O transport in eruptive plumes. Results of these simulations will be presented.

Zent, A. P.↗

DOE OSTI2023

Sources, seasonal cycling, and fate of plutonium in a seasonally stratified and radiologically contaminated pond

Unlike short-term laboratory experiments, studies at sites historically contaminated with radionuclides can provide insight into contaminant migration behavior at environmentally-relevant decadal timescales. One such site is Pond B, a seasonally stratified reservoir within Savannah River Site (SC, USA) has low levels (μBq L –1 ) of plutonium in the water column. Here, we evaluate the origin of plutonium using high-precision isotope measurements, investigate the impact of water column geochemistry on plutonium cycling during different stratification periods, and re-evaluate long-term mass balance of plutonium in the pond. New isotopic data confirm that reactor-derived plutonium overwhelms input from Northern Hemisphere fallout at this site. Two suggested mechanisms for observed plutonium cycling in the water column include: (1) reductive dissolution of sediment-derived Fe(III)-(oxyhydr)oxides during seasonal stratification and (2) plutonium stabilization complexed strongly to Fe(III)-particulate organic matter (POM) complexes. While plutonium may be mobilized to a limited extent by stratification and reductive dissolution, peak plutonium concentrations are in shallow waters and associated with Fe(III)-POM at the inception of stratification. This suggests that plutonium release from sediments during stratification is not the dominant mechanism driving plutonium cycling in the pond. Importantly, our analysis suggests that the majority is retained in shallow sediments and may become increasingly recalcitrant.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Digital Droplet PCR and Mesocosm-Based Methods to Evaluate Biocontainment Strategies in a Native Soil Ecosystem

Genetically modified industrial production microbes and their associated bioproducts have emerged as an integral component of a sustainable bioeconomy. However, the rapid development of these innovative technologies raises biosecurity concerns, namely, the risk of environmental escape. Thus, the realization of a bioeconomy hinges not only on the development and deployment of microbial production hosts, but also on the development of secure biosystems and biocontainment designs. Current laboratory-based biocontainment testing systems do not accurately reflect the complexities found in natural environments, necessitating an environmentally relevant analysis pipeline that allows for the detection of rare escapees within a complex soil microbiome and differentiation between closely related strains. To this end, we have developed an approach that utilizes soil mesocosms and integrated digital droplet PCR (ddPCR) system to evaluate the efficacy of novel biocontainment strategies. We demonstrate the utility of this approach by modeling contamination with industrial microbial chasses versus their biocontained counterparts. Here we demonstrate the broad utility of this system by highlighting findings from strains of Saccharomyces cerevisiae that are contained with an inducible toxin anti-toxin system, strains of Synechocystis sp. PCC 6803 contained via gene knockout or toxin anti-toxin system, and strains of Escherichia coli that are contained via genomic recoding. We also show that ddPCR can be used to detect gene copies from E. coli equal to those counted by traditional spot plating assays. The resultant data demonstrates that this system has broad utility across diverse microbial chassis and biocontainment strategies and enables researchers to track the fate of our contaminating microbe with high sensitivity in the soil. The findings presented here support the use of this mesocosm-based approach to assess the environmental impact of industrial microbes and to validate biocontainment strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Editorial for Special Issue “Environmentally Sound In Situ Recovery Mining of Uranium”

This Special Issue features seven articles that cover a range of topics pertaining to the environmentally sound in situ recovery mining of uranium (U ISR). The topics include: (1) methods for assessing the potential environmental impacts of future U ISR operations using historical operational records and available geohydrologic, geochemical and climate data in a specific regional setting; (2) laboratory column studies to parameterize a uranium surface complexation model that can be used to predict uranium fate and transport in groundwater; and (3) a field evaluation of both a chemical reductant and a biostimulant to promote reducing geochemical conditions after oxidative mining at a U ISR facility.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Trace explosive residue detection of HMX and RDX in post-detonation dust from an open-air environment

Explosives are often used in industry, geology, mining, and other applications, but it is not always clear what remains after a detonation or the fate and transport of any residual material. The goal of this study was to determine to what extent intact molecules of high explosive (HE) compounds are detectable and quantifiable from post-detonation dust and particulates in a field experiment with varied topography. We focused on HMX (1,3,5,7-Tetranitro-1,3,5,7-tetrazocane), which is less studied in field detonation literature, as the primary explosive material and RDX (1,3,5-Trinitroperhydro-1,3,5-triazine) as the secondary material. The experiment was conducted at Site 300, Lawrence Livermore National Laboratory’s Experimental Test Site, in California, USA. Two 20.4 kg and one 40.8 kg above ground explosions (primarily comprised of LX-14, an HMX-based polymer-bonded high explosive) were detonated on an open-air firing area on separate days. The complex terrain of the firing area (e.g., buildings, berm, low-height obstacles) was advantageous to study HE deposition in relation to plume dynamics. Three types of samples were collected up to 100 m away from each shot: surface swipes of aluminum plates, surface swipes of fixed objects, and filters from air samples. We used atmospheric flow tube-mass spectrometry (AFT-MS) to quantify picogram levels of molecular residue of HE material in the post-detonation dust. An aliquot of sample extract in methanol (e.g., 1 µL of 0.5 mL) was placed onto a resistive material and then thermally desorbed into the AFT-MS. We successfully detected and quantified both HMX and RDX in many of the samples. Based on mass (pg) detected and solution dilution, we back-calculated the mass collected on the swipe or filter (ng per sample). The aerial distribution of molecular residue was consistent with the path of the plume, which was strongly determined by wind speed and direction at the time of each shot. The quantity of material detected appeared to correlate more with distance from the shot and the wind conditions than with shot size. This study demonstrates that the picogram detection levels of AFT-MS are well-suited for quantification of analytes (e.g., HMX and RDX) in environmental samples.

atmospheric flow tube-mass spectrometry (AFT-MS), ↗

DOE OSTI2024

Water acidification aggravates lithium-induced toxicity represented by energy supply, oxidative stress, and cell fate in Daphnia magna neonates

Lithium is extensively utilized in industrial energy production, particularly in lithium-ion batteries, and in pharmaceuticals for the treating clinical mood disorders. Consequently, lithium is frequently detected in various environmental matrices. It has been reported to cause a range of toxic effects on aquatic organisms including oxidative stress, neurological disorders, and reproductive suppression. Water acidification is a global issue with numerous negative impacts on aquatic organisms. It can alter the physio-chemical properties and bioavailability of metal ions. The acidic leaching process during lithium battery treatment and global water acidification both suggest that lithium contamination often occurs in acidic environments. In the present study, Daphnia magna neonates were exposed to four treatments (control, lithium alone, low pH, and combined) to investigate whether an acidic environment exacerbates the toxic effects of lithium on aquatic organisms and to explore potential toxic action mechanisms. The results indicated that low pH posed a significant threat to the growth and reproduction of D. magna. When exposed to both lithium and low pH, there was increased lithium accumulation and an energy trade-off response, leading to increased energy allocation to reproduction and reduced energy for growth. Lithium exposure stimulated D. magna activity, while low pH inhibited it, suggesting that an imbalance in energy consumption and supply. Combined exposure to lithium and low pH resulted in severe oxidative stress due to mitochondrial dysfunction, under-utilization of energy substances, and increased ionic homeostasis disturbances. Consequently, the exposed organism altered apoptosis and autophagy processes to maintain homeostasis. In conclusion, the present study demonstrated that lithium and water acidification posed a population-level threat to D. magna, and their combined exposure significantly largely exacerbated the toxic effects.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗