Search NASA⌕ Search

SEARCH · Search NASA

Results for “Aqueous Chemistry”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Investigating the Impacts of Aqueous-Phase Processing on Organic Aerosol Chemical Climatology Using ARM and ASR Observations

This project improved understanding of how atmospheric aerosol particles form and evolve, with a focus on the role of water-driven (aqueous-phase) chemical reactions in the atmosphere. These processes occur in clouds, fog, and humid air and can significantly change the composition and properties of airborne particles, known as aerosols, which influence air quality and climate. By combining field measurements, laboratory experiments, and advanced analytical techniques, the project identified key chemical signatures that allow scientists to distinguish particles formed through aqueous processes from those formed in the gas phase. Observations from multiple environments, including wildfire smoke, urban regions, and cloud-influenced areas, show that aqueous chemistry is an important pathway for particle formation and aging. The project also developed new measurement approaches using uncrewed aerial systems (UAS) to capture how aerosol composition varies with altitude, providing critical insights into how particles interact with clouds. In addition, new data analysis frameworks were created to better interpret long-term aerosol measurements and improve characterization of particle sources and transformations. These results have been integrated into a global database of aerosol measurements and used to support atmospheric modeling efforts. Overall, the project provides important tools and knowledge to improve predictions of how aerosols affect climate and air quality, particularly through their interactions with radiation and clouds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Mechanistic mass transfer in hollow fiber membrane solvent extraction for bio-based isobutanol

Membrane solvent extraction (MSE) has emerged as a promising method for selectively recovering bioproducts from complex aqueous streams. Bio-isobutanol, a next-generation feedstock for biofuel, remains challenging to recover because of its low concentration and the presence of inhibitory substances. This study explores the potential of hollow fiber (HF) MSE for bio-isobutanol recovery and systematically examines the coupled effects of fiber packing, shell-side flow dynamics, and aqueous chemistry on performance. A resistance-in-series model is applied to understand mass transfer in the HF MSE modules, quantify local resistances, and validate overall performance. The results show that increasing the fiber packing provides a larger interfacial area but induces poor flow distribution and channeling, hindering effective isobutanol transport. Meanwhile, increasing the shell-side velocity improves isobutanol recovery due to reductions in the boundary layer thickness. The presence of salts, added to mimic fermentation broth, increases the partition coefficient through salting-out effects, further improving isobutanol flux. A modified correlation for the shell-side mass transfer coefficient (k s,ϕ+v ), integrating geometric and hydrodynamic effects, was developed and validated. The proposed model achieves highly predictive accuracy (r 2 = 0.9808) across a wide range of conditions, outperforming previous models. The findings provide mechanistic insight into the interaction of geometric packing, hydrodynamics, and chemistry in governing mass transfer in HF MSE. Overall, this work demonstrates the potential of HF MSE for efficient bio-isobutanol recovery and also provides practical guidelines on critical factors (packing fraction, partition coefficient, and shell-side velocity), aiding in the design and scaling of MSE systems for resource recovery.

Aqueous chemistry↗
DOE OSTI2026

Accessibility and Reactivity of Pentavalent Plutonium under Alkaline Conditions

Plutonium exhibits a particularly complex and rich aqueous chemistry due to a dynamic redox equilibrium that can result in the coexistence of four different oxidation states in aqueous solution. Within this equilibrium, pentavalent plutonium is among the most soluble and dominant oxidation states of Pu in neutral to alkaline aqueous solutions of relevance to environmental chemistries and the extreme chemical environments encountered in high-level radioactive wastes. Despite this, the fundamental chemistry of Pu­(V) under such conditions remains poorly understood. Here, in this study, we demonstrate the redox accessibility of Pu­(V) in alkaline media based on the observations of an electrochemically reversible Pu­(VI/V) couple at E 1/2 = 0.19 V vs Hg/HgO (0.29 V vs NHE), allowing us to electrolytically generate Pu­(V) in alkaline solution. These Pu­(V) solutions remained stable under ambient conditions for at least 9 days before precipitation of crystalline Na 2 [Pu V O 2 (OH) 3 ]·2H 2 O, the first structurally characterized Pu­(V) hydroxide. The modest potential of the Pu­(VI/V) redox couple allowed us to reproduce Na 2 [Pu V O 2 (OH) 3 ]·2H 2 O synthetically as well as isolate two additional novel Pu­(V)-bearing hydroxide phases Na­[Pu V O 2 (OH) 2 (H 2 O)]·2.5H 2 O and K 2 [Pu V O 2 (OH) 3 ]·2H 2 O as single crystals from alkaline reactions under mild hydrothermal conditions (<200 °C) using Na 2 O 2 and KO 2 as reductants. This reactivity is rationalized and informed by our electrochemical measurements. The properties of the Pu­(V) solids were further characterized by using vibrational and optical spectroscopy.

Kravchuk, Dmytro V. [Argonne National Laboratory (↗
DOE OSTI2025

Simulating Droplet-Resolved Haze and Cloud Chemistry Forming Secondary Organic Aerosols in Turbulent Conditions within Laboratory and Cloud Parcels

Most of our existing knowledge of cloud chemistry in regards to forming secondary organic aerosols (SOA) is based on measurements in bulk aqueous solutions. However, SOA reaction kinetics derived from bulk solution measurements might differ from the kinetics in actual cloud droplets, since turbulent mixing and ionic strengths, and ratio of surface area to volume in individual cloud droplets might vary substantially from bulk solutions in the real atmosphere. Three-dimensional models at various scales have been used to simulate aqueous chemistry. However, most of these models do not resolve turbulence down to the smallest length scales of 1 mm and do not simulate cloud chemistry in individual cloud droplets due to large computational costs. Here we incorporate the formation of isoprene epoxydiol SOA (IEPOX-SOA) in individual droplets within a one-dimensional explicit mixing parcel model (EMPM-Chem). We apply EMPM-Chem to simulate turbulence and droplet-resolved IEPOX-SOA formation using a configuration based on the Michigan Tech Pi chamber. We find that the dissolution of IEPOX gases is weighted more towards larger cloud droplets due to their large liquid water content (compared to smaller droplets), while the conversion of dissolved IEPOX to IEPOX-SOA is much greater within smaller deliquesced haze particles due to their higher acidity and ionic strengths compared to cloud droplets. We also find that as droplet residence times increase in the chamber, e.g., due to increasing ammonium bisulfate seed aerosol injection rates and/or increasing heights of the chamber, formation of IEPOX-SOA increases substantially. Thus, our EMPM-Chem model could be used to design future cloud chambers to maximize SOA production from cloud chemistry. We also apply the EMPM-Chem model to simulate how IEPOX-SOA formation evolves in individual cloud droplets within rising cloudy parcels in the atmosphere. We find that as subsaturated air is entrained into and turbulently mixed with the cloud parcel, evaporation causes a reduction in droplet sizes, which leads to corresponding increases in per droplet ionic strength and acidity. Increased droplet acidity in turn greatly accelerates the kinetics of IEPOX-SOA formation. In conclusion, our results provide key insights into single-cloud-droplet chemistry, suggesting that entrainment mixing may be an important process that increases SOA formation in the real atmosphere.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Control Selection for the Neutralization Tank in the Aqueous Recovery System at the Savannah River Plutonium Processing Facility

The Aqueous Recovery System (ARS) at the Savannah River Plutonium Processing Facility (SRPPF) recovers and purifies plutonium (Pu) using aqueous chemistry techniques. The neutralization tanks in the ARS collect waste streams with various impurities and greatly reduced concentrations of Pu than are produced during aqueous processing. Criticality safety is primarily achieved in the ARS by using geometrically favorable process vessels. However, due to the geometry of neutralization tanks, each tank is administratively limited to no more than 450 g Pu, thus representing the transition from geometry to mass control. To ensure that this mass limit is not exceeded, an administrative control requires taking two samples of any solution to be sent to a neutralization tank. Normal operations are expected to result in less than 50 g Pu in a neutralization tank filled to its capacity of 250 L. Process upsets may cause an inadvertent transfer of up to 1000 g Pu to a neutralization tank, producing a system that is potentially not subcritical for all possible configurations of the tank. To ensure that a neutralization tank remains safety subcritical, passive engineered controls (e.g. changing tank geometry or adding fixed poisons), active engineered controls (e.g. interlocks), and administrative controls (e.g. soluble poisons and valve isolation) were considered and their viability evaluated. Ultimately, the team chose an administrative, dual-valve isolation strategy. This paper will thoroughly discuss the various control strategy options and why many of the options were not feasible for maintaining criticality safety.

Dressman, Phillip M. [Savannah River Nuclear Solut↗
DOE OSTI2025

Control Selection for the Neutralization Tank in the Aqueous Recovery System at the Savannah River Plutonium Processing Facility

The Aqueous Recovery System (ARS) at the Savannah River Plutonium Processing Facility (SRPPF) recovers and purifies plutonium (Pu) using aqueous chemistry techniques. The neutralization tanks in the ARS collect the waste streams, containing various impurities and greatly reduced concentrations of Pu, that are produced during aqueous processing. Criticality safety is primarily achieved in the ARS by using geometrically favorable process vessels. However, due to the geometry of neutralization tanks, each tank is administratively limited to no more than 450 g Pu, thus representing the transition from geometry to mass control. To ensure that this mass limit is not exceeded, an administrative control requires taking two samples of any solution to be sent to a neutralization tank. Normal operations are expected to result in less than 50 g Pu in a neutralization tank filled to its capacity of 250 L. Process upsets may cause an inadvertent transfer of up to 1000 g Pu to a neutralization tank, producing a system that is potentially not subcritical for all possible configurations of the tank. To ensure that a neutralization tank remains safety subcritical, passive engineered controls (e.g.changing tank geometry or adding fixed poisons), active engineered controls (e.g. interlocks), and administrative controls (e.g. soluble poisons and valve isolation) were considered and their viability evaluated. Ultimately, the team chose an administrative, dual-valve isolation strategy. This paper will thoroughly discuss the various control strategy options and why many of the options were not feasible for maintaining criticality safety.

Dressman, Phillip M. [Savannah River Nuclear Solut↗
DOE OSTI2020

Opportunities of Aqueous Manganese-Based Batteries with Deposition and Stripping Chemistry

Rechargeable aqueous manganese-based batteries have been attracting significant attention owing to their advantages of low cost, high safety, and ease of manufacturing, which are promising attributes for grid-scale energy storage applications. However, most traditional manganese-based batteries with solid-state conversion and intercalation reactions suffer from low capacity and poor long-term cycling stability. The recent novel storage mechanism based on cathode Mn 2+ /MnO 2 deposition/stripping chemistry has fundamentally tackled these issues, enabling a new generation of manganese-based batteries with superior electrochemical performance. Here, the recent advances in aqueous manganese-based batteries with the Mn 2+ /MnO 2 deposition/stripping chemistry are reviewed. Furthermore, a summary of the development of manganese-based batteries with different storage mechanisms is provided and new opportunities for the emerging Mn 2+ /MnO 2 chemistry in the latest generation are highlighted. Then, the current understanding of the Mn 2+ /MnO 2 charge storage mechanism and its potential in manganese-based batteries for large-scale energy storage applications is presented. Moreover, insights into opportunities and future directions for manganese-based batteries with the Mn 2+ /MnO 2 chemistry are proposed.

25 ENERGY STORAGE↗
DOE OSTI2023

The combined effects of Mg 2+ and Sr 2+ incorporation during CaCO 3 precipitation and crystal growth

Calcite (CaCO 3 ) composition and properties are defined by the chemical environment in which CaCO 3 forms. However, a complete understanding of the relationship between aqueous chemistry during calcite precipitation and resulting chemical and physical CaCO 3 properties remains elusive; therefore, we present an investigation into the coupled effects of divalent cations Sr 2+ and Mg 2+ on CaCO 3 precipitation and subsequent crystal growth. Through chemical analysis of the aqueous phases and microscopy of the resulting calcite phases in compliment with density functional theory calculations, we elucidate the relationship between crystal growth and the resulting composition (elemental and isotopic) of calcite. The results of this experimental and modeling work suggest that Mg 2+ and Sr 2+ have cation-specific impacts that inhibit calcite crystal growth, including: (1) Sr 2+ incorporates more readily into calcite than Mg 2+ (D Sr > D Mg ), and increasing [Sr 2+ ] t or [Mg 2+ ] t increases D Sr ; (2) the inclusion of Mg 2+ into structure leads to a reduction in the calcite unit cell volume, whereas Sr 2+ leads to an expansion; (3) the inclusion of both Mg 2+ and Sr 2+ results in a distribution of unit cell impacts based on the relative positions of the Sr 2+ and Mg 2+ in the lattice. These experiments were conducted at saturation indices of CaCO 3 of ~4.1, favoring rapid precipitation. This rapid precipitation resulted in observed Sr isotope fractionation confirming Sr isotopic fractionation is dependent upon the precipitation rate. We further note that the precipitation and growth of calcite favors the incorporation of the lighter 86 Sr isotope over the heavier 87 Sr isotope, regardless of the initial solution conditions, and the degree of fractionation increases with D Sr . In sum, these results demonstrate the impact of solution environment to influence the incorporation behavior and crystal growth behavior of calcite. These factors are important to understand in order to effectively use geochemical signatures resulting from calcite precipitation or dissolution to gain specific information.

58 GEOSCIENCES↗
DOE OSTI2022

Water Defect Stabilizes the Bi 3+ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure

In this work, the aqueous hydration structure of Bi 3+ is probed using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations of ion-water clusters and of condensed-phase solutions. Anomalous features in the EXAFS spectra are found to be associated with a highly asymmetric first-solvent water shell. The aqueous chemistry and structure of the Bi 3+ ion is dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multi-modal distribution of waters in the first shell that are separated by about 0.2Å. The lone-pair structure is stabilized by a collective response of multiple waters that are localized near the lone-pair anti-bonding site. The findings indicate that the lone-pair stereochemistry of aqueous Bi 3+ plays a major role in the binding of water and ligands in aqueous solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Cloud Water Chemistry and Aerosol Processing: Assessing the Hydroxyl Radical Burst in Newly Formed Cloud Droplets (Field Campaign Report)

Aerosol particles are tiny liquid or solid particles in the atmosphere, ranging in size from a few nanometers to several micrometers in diameter. Aerosol-cloud interactions are the most uncertain aspect of the climate system, and models routinely underpredict aerosol particle formation. Clouds are well known to alter aerosol size, chemical composition, and radiative properties, but the processes are poorly characterized. Organics and sulfates are the most abundant materials in particles, and for each of these there are significant gaps in the understanding of the role of clouds in their formation and/or aging. Many of the cloud processes are driven by aqueous chemistry that depends on hydroxyl (OH) radicals, the subject of this project.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Effect of oxidation on the release of multiple metals from industrially polluted sediments and synchrotron-based evidence of Cu–S dynamic association

Disposal operations for industrially polluted sediments are usually accompanied by disturbance and resuspension, which can induce metal remobilization and secondary pollution. Evaluating the risk of metal release under various redox conditions is fundamental for predicting contaminant mobilization and guiding remediation measures. An abandoned oxidation pond, Yanjia Lake, China, was selected as a typical industrially polluted site. Re-suspension experiments were carried out by mixing polluted sediments with lake water under oxic or anoxic conditions, then investigating the effect of oxidation conditions on the release of multiple metals. Metal concentrations and aqueous chemistry in the overlying water were monitored. Synchrotron-based methods, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), were used to characterize oxidation states and coordination conditions of metals in sediments. The release of metals, including Cr, Co, Ni, Cu, Zn, Se, Mo, Sn, Cd, and Pb, was enhanced under oxic vs. anoxic conditions. The XANES analysis revealed that elevated Cr and Zn concentrations under oxic conditions likely resulted from the oxidation of Cr(III) and oxidizing dissolution of ZnS, respectively. K-edge Cu XANES, S XANES, and Cu EXAFS analyses reconstructed the Cu–S association, indicating that S-related oxidation promoted Cu release and Cu–O partly replaced Cu–S in the sediment after a 7-day oxic treatment. The release of most metals was promoted under oxic conditions, resulting from the oxidation of sulfides and metals as indicated by aqueous and synchrotron-based evidence. The risk of secondary pollution is greatly enhanced under oxic conditions, which suggests that measures should be taken to minimize the redox disturbance during sediment remediation. This information can guide the management of sediments in Yanjia Lake and other contaminated sites with similar properties.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Flexible Copper Metal Circuits via Desktop Laser Printed Masks

A novel process is demonstrated that produces patterns of electrically conductive copper on a flexible polyimide film substrate using standard desktop laser printed toner and near room temperature aqueous chemistry. The laser toner acts as a mask to selectively block the ion exchange self-metallization (IESM) reduction reaction that forms nanoscale silver or palladium coatings at the polyimide surface. The silver or palladium IESM coating is then used as a catalyst for electroless deposition of copper. Under appropriate conditions, the copper is deposited selectively on top of the catalyst layer. The resulting copper layer has a measured sheet resistance as low as 0.3 Ohms/sq. Electrical isolation was measured between copper traces spaced as close as 300 microns, and high conductivity was measured along traces with widths as low as 200 microns. The minimum pattern size appears to be limited primarily by the resolution of the laser toner pattern, as the IESM metal layer was observed to follow the contours of individual toner particles. Here, the process avoids the use of high temperature, vacuum, and organic solvents and is thus suitable for very low cost prototyping or distributed manufacturing of simple electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Microbially mediated iron redox cycling of subsurface sediments from Hanford Site, Washington State, USA

Iron-bearing clay minerals are predominant in soils and sediments, and they undergo oxidation-reduction cycles as a result of natural processes such as wetting/drying cycles and plant root respiration. However, the kinetics and mechanisms of multiple redox cycles of iron in clay-rich sediments and consequences of such cycling on sediment properties are poorly understood. The objective of this study was to understand how multiple redox cycles of Fe in clay-rich sediment affect the rate and extent of Fe bioreduction and the physicochemical properties of the sediment. A natural sediment sample containing Fe-bearing montmorillonite from Hanford, Washington, USA was size-fractionated [2.0 to 0.5 μm (Hanford-C) and 0.5 to 0.02 μm (Hanford-F)] and redox-cycled for four times. Bioreduction was achieved utilizing Geobacter sulfurreducens and re-oxidization was performed with sparged air. Time-course change of total Fe (II) was monitored to measure the rate and extent of Fe (III) bioreduction. Redox-cycled sediments were characterized to determine the physicochemical changes. Both the initial rate and extent of bioreduction fluctuated across the four redox cycles, but they ultimately decreased from 5.3 μmol g -1 h -1 and 22.9% to nearly zero by the fourth cycle. These fluctuation patterns were likely due to a combined effect of reductive dissolution of small/poorly crystalline clay particles (by 3–5%) and clay mineral structural changes, as evidenced by redox induced changes of aqueous chemistry, surface area, cation exchange capacity, mineralogy, and Mössbauer parameters. Once these small/poorly crystalline clay particles were dissolved, structural Fe in residual larger and more crystalline clay particles was largely reversible across additional redox cycles, as revealed by Mössbauer spectroscopy through the first three cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Major element composition controls rare earth element solubility during leaching of coal fly ash and coal by-products

Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibly sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

A coarse-grained model of clay colloidal aggregation and consolidation with explicit representation of the electrical double layer

The aggregation of clay minerals in liquid water exemplifies colloidal self-assembly in nature. These negatively charged aluminosilicate platelets interact through multiple mechanisms with different sensitivities to particle shape, surface charge, aqueous chemistry, and interparticle distance and exhibit complex aggregation structures. Experiments have difficulty resolving the associated colloidal assemblages at the scale of individual particles. Conversely, all-atom molecular dynamics (MD) simulations provide detailed insight on clay colloidal interaction mechanisms, but they are limited to systems containing a few particles. We develop a new coarse-grained (CG) model capable of representing assemblages of hundreds of clay particles with accuracy approaching that of MD simulations, at a fraction of the computational cost. Our CG model is parameterized based on MD simulations of a pair of smectite clay particles in liquid water. A distinctive feature of our model is that it explicitly represents the electrical double layer (EDL), i.e., the cloud of charge-compensating cations that surrounds the clay particles. Our model captures the simultaneous importance of long-range colloidal interactions (i.e., interactions consistent with simplified analytical models, already included in extant clay CG models) and short-range interactions such as ion correlation and surface and ion hydration effects. The resulting simulations correctly predict, at low solid-water ratios, the existence of ordered arrangements of parallel particles separated by water films with a thickness up to ~10 nm and, at high solid-water ratios, the coexistence of crystalline and osmotic swelling states, in agreement with experimental observations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Post-remediation geophysical assessment: Investigating long-term electrical geophysical signatures resulting from bioremediation at a chlorinated solvent contaminated site

There is a growing need to assess long-term impacts of active remediation strategies on treated aquifers. A variety of biogeochemical alterations can result from interactions of the amendment with the aquifer, conceivably leading to a geophysical footprint of the long-term alteration of an aquifer. This concept of post-remediation geophysical assessment was investigated in a shallow, chlorinated solvent-contaminated aquifer six to eight years after amendment delivery. Surface resistivity imaging and cross-borehole resistivity and induced polarization (IP) imaging were performed on a transect that spanned treated and untreated zones of the aquifer. Established relationships between IP parameters and surface electrical conductivity were used to predict vertical profiles of electrolytic conductivity and surface conductivity from the inverted cross-borehole images. Aqueous geochemistry data, along with natural gamma and magnetic susceptibility logs, were used to constrain the interpretation. The electrical conductivity structure determined from surface and borehole imaging was foremost controlled by the electrolytic conductivity of the interconnected pore space, being linearly related to fluid specific conductance. The electrolytic conductivity (and thus the conductivity images alone) did not discriminate between treated and untreated zones of the aquifer. In contrast, inverted phase angles and surface conductivities did discriminate between treated and untreated zones of the aquifer, with the treated zone being up to an order of magnitude more polarizable in places. Supporting aqueous chemistry and borehole logging datasets indicate that this geophysical footprint of the long-term impact of the remediation on the aquifer is most likely associated with the formation of polarizable, dispersed iron sulfide minerals. The study opens the door to the possibility of employing time-lapse electrical geophysical measurements to assist with long-term environmental stewardship of legacy sites undergoing active remediation.

bioremediation↗
DOE OSTI2024

Mineral-associated organic matter is heterogeneous and structured by hydrophobic, charged, and polar interactions

The formation of mineral-associated organic matter (MAOM) is a key phenomenon that may explain the slow turnover rates of carbon in soil organic matter (SOM). Despite this, important details pertaining to the structure and dynamics of MAOM remain unknown. In the present study, we use replica-exchange molecular dynamics simulations to gain insight into the structure of MAOM on the surface of prototypical phyllosilicate clay and Fe-oxide minerals, montmorillonite and goethite, fine-grained minerals that strongly impact soil carbon dynamics in temperate and tropical regions, respectively. We examine the impact of aqueous chemistry through the presence of either Na + or Ca 2 + charge balancing counterions. Our results are consistent with the hypothesized multilayer sorption (“onion-skin”) model of MAOM and help to explain previous observations regarding the patchy distribution of SOM on mineral surfaces. In particular, the SOM coatings are partial and laterally heterogeneous, and water retains extensive access to mineral surfaces even when significant SOM sorption occurs. Low molecular weight neutral SOM molecules ( < 200 Da) infrequently interact with the mineral surfaces nor their sorbed organic matter coatings and are increasingly labile with decreasing molecular weight. This observation is inconsistent with a central feature of the predominant soil continuum model of SOM and suggests that further iterations of the conceptual model may be required.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

[ 89 Zr]Zr-DFO-TOC: a novel radiopharmaceutical for PET imaging of somatostatin receptor positive neuroendocrine tumors

Neuroendocrine tumors (NETs) are clinically diverse types of tumors that can arise anywhere in the body. Previous studies have shown that somatostatin receptors (SSTRs) are overexpressed on NET cell membranes relative to healthy tissue, allowing for tumor targeting through radiolabeled somatostatin analogs (SSAs). This work aims to develop a novel 89 Zr-labeled tracer incorporating the SSA, octreotide (TOC), for positron emission tomography (PET) imaging of SSTR + NETs and predictive dosimetry calculations, leveraging the excellent nuclear (t ½ = 3.27 days, β+ = 22.3%, β + avg = 395.5 keV) and chemical characteristics (+ 4 oxidation state, preferential coordination number of 7/8, favorable aqueous chemistry) of 89 Zr. In combination with 89 Zr, the known radiochemistry with the chelator deferoxamine (DFO) gives reason to believe that this radiopharmaceutical incorporating an octreotide conjugate will be successful in studying the suitability of detecting SSTR + NETs.

62 RADIOLOGY AND NUCLEAR MEDICINE↗