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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

AstroBioLab: A Mobile Biotic and Soil Analysis Laboratory

The Jet Propulsion Laboratory, Scripps Institution of Oceanography, and NASA Ames Research Center are currently developing a mobile Astrobiology Laboratory (AstroBioLab) for a series of field campaigns using the Chilean Atacama Desert as a Martian surface analog site. The Astrobiology Science and Technology for Exploring Planets (ASTEP) program funded AstroBioLab is designed around the Mars Organic Detector (MOD) instrument and the Mars Oxidant Instrument (MOI) which provide complementary data sets. Using this suite of Mars Instrument Development Program (MIDP) and Planetary Instrument Definition and Development Program (PIDDP) derived in situ instruments, which provide state-of-the-art organic compound detection (attomolar sensitivity) and depth profiling of oxidation chemistry, we measure and correlate the interplay of organic compounds, inorganic oxidants, UV irradiation and water abundance. This mobile laboratory studies the proposition that intense UV irradiation coupled with low levels of liquid water generates metastable oxidizing species that can consume moderate amounts of seeded organic compounds. Results from the initial spring 2003 field campaign will be presented.

J L Bada↗
NASA NTRS2015

The Effect of Surface Chemical Functionality Upon Ice Adhesion

In nature, anti-freeze proteins present in fish utilize specific organic functionalities to disrupt ice crystal formation and propagation. Based on these structures, surfaces with controlled chemical functionality and chain length were evaluated both experimentally and computationally to assess the effect of both parameters in mitigating ice formation. Linear aliphatic dimethylethoxysilanes terminated with methyl or hydroxyl groups were prepared, characterized, and used to coat aluminum. The effect upon icing using a microdroplet freezing apparatus and the Adverse Environment Rotor Test Stand found hydroxyl-terminated materials exhibited a greater propensity for ice formation and adhesion. Molecular dynamics simulations of a silica substrate bearing functionalized species of similar composition were brought into contact with a pre-equilibrated ice crystal. Several parameters including chain mobility were monitored to ascertain the size of a quasi-liquid layer. The studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition.

Smith, Joseph G., Jr.↗
DOE OSTI2020

The Argonne SuperGel for CBRN Decontamination - 20160

The Argonne SuperGel was developed between 2003 and 2015 to fill a gap in our nation's capability to quickly decontaminate important structures following a radiological or nuclear release event. Specifically, the decontamination technology was developed to minimize damage to monuments, high valued structures, and critical infrastructure while reducing environmental and health impacts. An important criterion during its development, common reagents were employed that could be easily acquired in order to minimize the timeline for its deployment. Its current formulation uses off-the-shelf super-absorbing hydrogels common to the food and agricultural industry and common salts. Over the years, two formulations of the Argonne SuperGel have been developed to specifically target radioactive cesium contaminations and then, more generically, actinide and fission product contaminations. A biodegradable derivative of phosphoric acid is used in small amounts to promote the removal of insoluble actinide species. The original order of unit operations for the SuperGel technology was 1) applying the wash solution to promote mobility of the contaminants on the surface, 2) applying the hydrogel to absorb the wash solution and contaminants, and 3) removing the hydrogel for disposal. During the course of our studies, we tested a new formulation of the gel technology that eliminated the need for a separate step to apply the wash solution without a compromise in decontamination factors. Greater than 70% and >95% of Cs-137 were removed from concrete and tile coupons, respectively, after two decontaminations, with the best results using wash solutions of 1.0 M KCl and 1.0 M NH{sub 4}Cl formulations. We found no statistical difference between results at 30 deg. C and 40 deg. C or at 70% and 90% relative humidity. We tested the gel under strong UV irradiation to simulate extreme environments. While a tropical noontime UV flux did not adversely affect the gel system decontamination of Cs-137 from concrete or tile coupons, the noontime flux resulted in significant dehydration of the gel after two hours of constant exposure. The rehydration of the gel by the humid air (at 90% humidity and 40 deg. C) was slow and may not be sufficient to offset dehydration by the sun. Americium decontamination from concrete was 70% after optimizing the phosphoric acid derivative and carbonate salt concentration in the wash solution. Since its development, we have had the opportunity to test the SuperGel in the removal of legacy contaminations in hot cell facilities and former glovebox facilities at Argonne. This has provided a unique opportunity to evaluate the SuperGel on a range of contaminants outside the original specifications for its use. We will report on the origin of the gel formulation, some highlighted experimental data including independent testing by the US EPA which has never been reported, and its efficacy for removing legacy alpha contaminations and its potential use for removal of chemical and biological hazardous agents. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Multimodal, microspectroscopic speciation of legacy phosphorus in two US mid-Atlantic agricultural soils

To understand phosphorus (P) mobility in agricultural soils and its potential environmental risk, it is essential to directly measure solid phase P speciation. Often, bulk P K-edge X-ray absorption near edge structure (XANES) spectroscopy followed by linear combination fitting (LCF) is utilized to determine the solid P phases in soil. However, this method may limit results to only a few major phases. Additionally, XANES spectra for different P species may have very similar features, leading to an over- or underestimate of their contribution to LCF. Here, an improved P speciation by pairing multimodal microbeam-X-ray fluorescence (µ-XRF) mapping coupled with µ-XANES (microbeam-X-ray absorption near edge structure) analysis to directly speciate major and minor P phases on the micron scale is provided. We combined maps of both tender (P, sulfur, aluminum, and silicon) and hard energy (calcium, iron [Fe], and manganese) elements to evaluate the elemental co-locations with P. To better account for uncertainty assigning XANES peaks to individual compounds, a more quantitative fingerprinting by “spectral feature analysis” was completed. With this analysis, an R-factor is reported for the fit. These results were compared to traditional LCF. Pre-edge fitting results revealed the presence of a two-component pre-edge feature for phosphate adsorbed to ferrihydrite. Additionally, phytate co-precipitated with ferrihydrite (Phytate-Fe-Cop) had a pre-edge feature, indicating direct association with Fe. Lastly, a unique P species associated with manganese oxide was identified in the soil via multimodal mapping and µ-XANES. These results allow for better prediction of P dissolution and mobility.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Bulk Glassy GeTe 2 : A Missing Member of the Tetrahedral GeX 2 Family and a Precursor for the Next Generation of Phase-Change Materials

Vitreous germanium disulfide GeS 2 and diselenide GeSe 2 belong to canonical chalcogenide glasses extensively studied over the past half century. Their high-temperature orthorhombic polymorphs are congruently melting compounds, and the tetrahedral crystal and glass structure is largely preserved in the melt. In contrast, the ditelluride counterpart is absent in the Ge-Te phase diagram, which shows only a single compound, monotelluride GeTe. Phase-change materials based on GeTe have become a technologically important class of solids, and their structure and properties are also widely studied. Surprisingly, very scarce information is available for alloys having GeTe 2 stoichiometry. Using a fast quenching procedure in silica capillaries, high-energy X-ray diffraction, and Raman spectroscopy supported by first-principles simulations, we show that bulk glassy GeTe 2 differs substantially from the lighter GeX 2 members, revealing 46% of trigonal germanium, 31% of three-fold coordinated tellurium, and only 20% of edge-sharing tetrahedra or pyramids. The fraction of homopolar Ge-Ge bonds is low; however, the population of dominant Te-Te dimers and Te n oligomers, n <= 10, appears to be significant. The complex structural and chemical topology of g-GeTe 2 is directly related to the thermodynamic metastability of germanium ditelluride, schematically represented by the following reaction: GeTe 2 $\rightleftarrows$ GeTe + Te. Disproportionation is complete above liquidus in the temperature range of semiconductor-metal transition, and the dense metallic GeTe 2 liquid, mostly consisting of five-fold coordinated Ge species, exhibits high fluidity, strong fragility (m = 99 ± 5), and presumably a fast structural transformation rate combined with low atomic mobility in the vicinity of the glass transition temperature, favorable for reliable long-term data retention in nonvolatile memories. The observed and predicted characteristic features make GeTe 2 a promising precursor for the next generation of phase-change materials, especially coupled with additional metal doping, depolymerizing the tetrahedral interconnected glass network and accelerating (sub)nanosecond crystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

AutoCCS: automated collision cross-section calculation software for ion mobility spectrometry–mass spectrometry

Abstract Motivation Ion mobility spectrometry (IMS) separations are increasingly used in conjunction with mass spectrometry (MS) for separation and characterization of ionized molecular species. Information obtained from IMS measurements includes the ion’s collision cross section (CCS), which reflects its size and structure and constitutes a descriptor for distinguishing similar species in mixtures that cannot be separated using conventional approaches. Incorporating CCS into MS-based workflows can improve the specificity and confidence of molecular identification. At present, there is no automated, open-source pipeline for determining CCS of analyte ions in both targeted and untargeted fashion, and intensive user-assisted processing with vendor software and manual evaluation is often required. Results We present AutoCCS, an open-source software to rapidly determine CCS values from IMS-MS measurements. We conducted various IMS experiments in different formats to demonstrate the flexibility of AutoCCS for automated CCS calculation: (i) stepped-field methods for drift tube-based IMS (DTIMS), (ii) single-field methods for DTIMS (supporting two calibration methods: a standard and a new enhanced method) and (iii) linear calibration for Bruker timsTOF and non-linear calibration methods for traveling wave based-IMS in Waters Synapt and Structures for Lossless Ion Manipulations. We demonstrated that AutoCCS offers an accurate and reproducible determination of CCS for both standard and unknown analyte ions in various IMS-MS platforms, IMS-field methods, ionization modes and collision gases, without requiring manual processing. Availability and implementation https://github.com/PNNL-Comp-Mass-Spec/AutoCCS. Supplementary information Supplementary data are available at Bioinformatics online. Demo datasets are publicly available at MassIVE (Dataset ID: MSV000085979).

47 OTHER INSTRUMENTATION↗
NASA NTRS1987

The role of electronic mechanisms in surface erosion and glow phenomena

Experimental studies of desorption induced by electronic transitions (DIET) are described. Such studies are producing an increasingly complete picture of the dynamical pathways through which incident electronic energy is absorbed and rechanneled to produce macroscopic erosion and glow. These mechanistic studies can determine rate constants for erosion and glow processes in model materials and provide valuable guidance in materials selection and development. Extensive experiments with electron, photon, and heavy particle irradiation of alkali halides and other simple model materials have produced evidence showing that: (1) surface erosion, consisting primarily in the ejection or desorption of ground-state neutral atoms, occurs with large efficiencies for all irradiated species; (2) surface glow, resulting from the radiative decay of desorbed atoms, likewise occurs for all irradiating species; (3) the typical mechanism for ground-state neutral desorption is exciton formation, followed by relaxation to a permanent, mobile electronic defect which is the precursor to bond-breaking in the surface or near-surface bulk of the material; and (4) the mechanisms for excited atom formation may include curve crossing in atomic collisions, interactions with surface defect or impurity states, or defect diffusion.

Haglund, Richard F., Jr.↗
DOE OSTI2020

Immobilizing Pertechnetate in Ettringite via Sulfate Substitution

Until recently, a nuclear waste form did not exist for the immobilization and long-term storage of the anionic form of radionuclide technetium-99 (99Tc), pertechnetate (TcO 4 - ). Across international nuclear waste sites, the inability to capture TcO 4 - poses a threat to the local environment due to the anion’s long half-life and environmental mobility under environmentally oxic conditions. To combat this challenge, most waste forms would capture 99Tc using materials that reduce TcO 4 - to Tc(IV) species, e.g. 99Tc oxides or 99Tc sulfides. However, this is a short-lived solution unless reducing capacities can be regenerated to last over the long life expectancy of some nuclear waste forms (~10,000 years). In light of recent experimental observations gained from the development of cementitious waste forms and unconfirmed hypotheses from the literature, this work explores how ettringite, a common mineral formed in cementitious materials with demonstrated success in incorporating oxyanions, may be used to immobilize TcO 4 - directly and over the life-time of the waste form. Using batch precipitation experiments, solid phase characterization techniques, and ab initio molecular dynamics simulations, we demonstrate herein successful incorporation of TcO 4 - into ettringite via substitution for SO 4 2- within the ettringite crystal structure. Here, these results are first of their kind and confirm the hypothesis that ettringite acts as an immobilizing mineral within cementitious waste forms for the highly mobile TcO 4 - oxyanion, enhancing the overall performance of these waste forms over time.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Development of interatomic potential and effect of ordering on defect properties in CrMnV

Developing materials that can withstand extreme environments, such as high radiation doses and elevated temperatures, is crucial for next-generation particle accelerators, including the 2.4 MW Long-Baseline Neutrino Facility. High-Entropy Alloys have emerged as promising candidates for beam window materials due to their superior mechanical strength, corrosion resistance, and radiation tolerance. In this study, we focus on the Cr–Mn–V alloy system, developing and employing machine-learning interatomic potentials (MLIPs) to investigate the formation of an ordered phase and its influence on defect properties. Using hybrid Monte Carlo-Molecular Dynamics simulations, we observe the formation of a B2-ordered phase at lower temperatures, consistent with Density Functional Theory (DFT) predictions. Ordered structures display a bimodal distribution of migration energies and reduced mean square displacement values, indicating suppressed vacancy diffusion. Our results also show that the migration energy barrier varies based on the atomic species, with Mn and V exhibiting the highest and lowest average barriers, respectively. These findings suggest that atomic ordering inhibits defect mobility, potentially enhancing the radiation resistance of CrMnV alloys. The validated MLIP provides a reliable framework for simulations that are faster than traditional DFT while maintaining the accuracy required to study defect and ordering properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Total Column Infrared Trace Species in Baltimore Field Campaign Report

The U.S. Department of Energy’s Atmospheric Radiation Measurement (ARM) User Facility Coast-Urban-Rural Atmospheric Gradient Experiment (CoURAGE), including the first ARM Mobile Facility (AMF1), occurred during 2025 at a site in Baltimore, Maryland owned by Morgan State University. Our goal was to supplement the measurements taken by locating a Bruker EM27/SUN spectrometer at the site to make total column measurements of trace gases in the near-infrared. This EM27 location was one of six locations in the Washington, D.C./Maryland region during the summer of 2025, and the network of observations was intended to help us better understand emissions in the region, as well as how emissions interact with meteorology to affect air quality and other atmospheric attributes.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2005

Chemistry and Mineralogy of Outcrops at Meridiani Planum

Analyses of outcrops created by the impact craters Endurance, Fram and Eagle reveal the broad lateral continuity of chemical sediments at the Meridiani Planum exploration site on Mars. Approximately ten mineralogical components are implied in these salt-rich silicic sediments, from measurements by instruments on the Opportunity rover. Compositional trends in an apparently intact vertical stratigraphic sequence at the Karatepe West ingress point at Endurance crater are consistent with non-uniform deposition or with subsequent migration of mobile salt components, dominated by sulfates of magnesium. Striking variations in Cl and enrichments of Br, combined with diversity in sulfate species, provide further evidence of episodes during which temperatures, pH, and water to rock ratios underwent significant change. To first order, the sedimentary sequence examined to date is consistent with a uniform reference composition, modified by movement of major sulfates upward and of minor chlorides downward. This reference composition has similarities to martian soils, supplemented by sulfate anion and the alteration products of mafic igneous minerals. Lesser cementation in lower stratigraphic units is reflected in decreased energies for grinding with the Rock Abrasion Tool. Survival of soluble salts in exposed outcrop is most easily explained by absence of episodes of liquid H2O in this region since the time of crater formation.

Clark, B. C.↗
DOE OSTI2022

Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach

Solid-state NMR experiments on 2 H, 31 P, 13 C, and 1 H nuclei, including 31 P T 1 , 1 H T 1 , and 1 H T 1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D 2 O and/or CD 3 OD. The 13 C{ 1 H} CP MAS NMR experiment performed for compound 1-CD 3 OD (Zr (HPO 4 ) 2 .0.2CD 3 OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2 H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD 3 rotations around the C 3 -axis. It has been demonstrated that the intercalated species, D 2 O and CD 3 OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Here, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.

1H↗
NASA NTRS1995

A Helium GC/IMS for the Analysis of Extraterrestrial Volatiles in Exobiology Flight Experiments

For exobiology experiments on board spacecraft or space probes, a wide range of chemical species often must be detected and identified. The limited amount of power and space available for flight instruments severely limits the number of instruments that can be flown on any given mission. It is important then, that these experiments utilize instrumentation with universal response, so that all species of interest can be analyzed. Instrumentation to fulfill the analytical requirements of exobiology experiments has been developed utilizing Gas Chromatography - Ion Mobility Spectrometry. The Gas Chromatograph (GC) combines columns developed specifically for the complex mixtures anticipated with highly sensitive Metastable Ionization Detectors (a type of Helium Ionization Detector). To satisfy the limitations placed on resources, the Ion Mobility Spectrometer (IMS) uses the same ultra high purity helium as the GC. This GC-MS provides the analytical capability to fulfill a wide range of exobiology flight experiment applications and has been included on a proposed Discovery Mission and proposals for both Lander and Orbiter of the European Space Agency's Rosetta Comet Mission. A data base of helium IMS spectra is now being built for these future applications.

Kojiro, Daniel R.↗
DOE OSTI2024

Machine-learning-assisted deciphering of microstructural effects on ionic transport in composite materials: A case study of Li 7 La 3 Zr 2 O 12 -LiCoO 2

The effective diffusivity of ionic species in multiphase materials is critical for the design and function of composite materials for electrochemical energy storage. In practice, effective diffusivity depends sensitively not only on the intrinsic diffusivities of constituting materials but also on their topological arrangement; nevertheless, these coupled contributions are oversimplified in most analytical models. Here, we combine atomistically informed mesoscale modeling and machine learning (ML) analysis to unravel how such features affect effective diffusivity in two-phase composites. Using the Li 7 La 3 Zr 2 O 12 -LiCoO 2 composite solid-state battery cathode as a model system, we compute effective diffusivity for 600 distinct dense polycrystalline microstructures with different topological configurations of grains, grain boundaries, and heterointerfaces. We verify that in addition to atomic-scale variabilities, microstructural feature diversity can significantly impact effective transport properties. Across the ensemble of test microstructures, this often results in bimodal distributions of effective diffusivity that encompass two qualitatively distinct operating mechanisms, which we identify via flux analysis. An ML approach reveals that the most critical determining factors for effective diffusivity are the connectivity of bulk phases and their heterointerfaces. The role of ionic mobility at the heterointerfaces is also discussed. These insights highlight the combined importance of microstructure and interface engineering in tuning the transport properties of ionic species in composite materials. In conclusion, our framework can also be extended for understanding generic microstructure-property relationships in other complex multiphase materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Interactive effects of salinity, redox, and colloids on greenhouse gas production and carbon mobility in coastal wetland soils

Coastal wetlands, including freshwater systems near large lakes, rapidly bury carbon, but less is known about how they transport carbon either to marine and lake environments or to the atmosphere as greenhouse gases (GHGs) such as carbon dioxide and methane. This study examines how GHG production and organic matter (OM) mobility in coastal wetland soils vary with the availability of oxygen and other terminal electron acceptors. We also evaluated how OM and redox-sensitive species varied across different size fractions: particulates (0.45–1μm), fine colloids (0.1–0.45μm), and nano particulates plus truly soluble (<0.1μm; NP+S) during 21-day aerobic and anaerobic slurry incubations. Soils were collected from the center of a freshwater coastal wetland (FW-C) in Lake Erie, the upland-wetland edge of the same wetland (FW-E), and the center of a saline coastal wetland (SW-C) in the Pacific Northwest, USA. Anaerobic methane production for FW-E soils were 47 and 27,537 times greater than FW-C and SW-C soils, respectively. High Fe 2+ and dissolved sulfate concentrations in FW-C and SW-C soils suggest that iron and/or sulfate reduction inhibited methanogenesis. Aerobic CO 2 production was highest for both freshwater soils, which had a higher proportion of OM in the NP+S fraction (64±28% and 70±10% for FW-C and FW-E, respectively) and organic C:N ratios reflective of microbial detritus (5.3±5.3 and 5.3±7.0 for FW-E and FW-C, respectively) compared to SW-C, which had a higher fraction of particulate (58±9%) and fine colloidal (19±7%) OM and organic C:N ratios reflective of vegetation detritus (11.4 ± 1.7). The variability in GHG production and shifts in OM size fractionation and composition observed across freshwater and saline soils collected within individual and across different sites reinforce the high spatial variability in the processes controlling OM stability, mobility, and bioavailability in coastal wetland soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Hydrothermal solution calorimetry in acidic aqueous solutions and revisiting the standard partial molal thermodynamic properties of Nd 3+ from 25 to 300 °C

The mobility of rare earth elements (REE) can be predicted in aqueous fluids using geochemical modeling but the accuracy of these models strongly depends on the availability of robust thermodynamic properties for the REE aqueous species. The REE 3+ aqua ions are important in the derivation of the formation constants of all the major REE complexes including the chloride, sulfate, and fluoride species which predominate in many hydrothermal-magmatic systems. However, the thermodynamic properties of the REE 3+ aqua ions are still commonly derived from the Helgeson-Kirkham-Flowers (HKF) equation of state parameters tabulated several decades ago. The standard state thermodynamic properties at reference conditions (25 °C and 1bar) and their extrapolations to high temperature need to be verified, if not revised, based on hydrothermal experiments. In this study, the enthalpy of solution was measured for synthetic Nd hydroxide from 25 to 150 ºC to retrieve the standard partial molal thermodynamic properties of Nd 3+ as a function of temperature. The experiments were conducted in aqueous perchloric acid based solutions with starting pH of 2 and varying ionic strength (0.01 to 0.09 mol/kg NaClO 4 ). The standard partial molal enthalpy of formation (Δ f H°) of Nd 3+ derived from the experimental study displays differences of up to 10 kJ/mol compared to the enthalpy values derived from the HKF equation of state in the studied temperature range. These inaccuracies are resolved by adjusting the standard partial molal Gibbs energy of formation (Δ f G°) of Nd 3+ at 25 °C and 1 bar from -672.0 to -679.7 kJ/mol. The heat capacity function (C p °) derived between 25 and 150 ºC can be described by: C p ° = a 0 + a 1 ·T + a 2 ·T -2 , with a 0 = 1256, a 1 = -2.68, a 2 = -55.56·10 6 and T in Kelvin. A set of recommended thermodynamic properties is provided for the Nd 3+ aqua ions and corrections are provided for the chloride and fluoride species to remain internally consistent with the experimentally derived properties. These results allow predicting accurately the solubility of monazite between 25 and 300 ºC. Before these corrections, the properties for the Nd 3+ aqua ions derived from the HKF parameters resulted in up to ~1.5 orders of magnitude lower monazite solubility than determined experimentally. Here, a revision of the REE +3 aqua ions properties is necessary to accurately predict the mobility of REE in hydrothermal acidic solutions.

58 GEOSCIENCES↗
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 OSTI2025

Extraction of Terpenoids from Pine Needle Biomass Using Dimethyl Ether

Pine needles are an industrial feedstock for extracts used in a variety of applications, but conventional extraction methods often result in a degradation of the terpenoid compounds that naturally occur in loblolly pine ( Pinus taeda ). Separation of these compounds from pine biomass is an energy-intensive operation, typically requiring a significant input of thermal energy. An alternative separation approach with potential energy savings is extraction with a condensable gas, namely, dimethyl ether. Biomass materials are exposed to liquid dimethyl ether under pressure, which mobilizes the organics. The extract is then separated from the insoluble pine matter, and dimethyl ether is volatilized away from the separated organic species. A variety of terpene derivatives were extracted from pine needle biomass using this approach, including monoterpenes, sesquiterpenes, and related oxygenates, which were identified using two-dimensional gas chromatography/mass spectrometry. Additionally, the dimethyl ether-treated needles resemble needles subjected to low-temperature drying, whereas needles treated with a high-temperature drying method appear to have shrunken structures. The results suggest that dimethyl ether extraction has significant potential for separating valuable organics from complex matrices without the application of thermal energy during treatment.

dimethyl ether (DME) extraction↗