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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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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Interfacial and Activation Energies of Environmentally Abundant Heterogeneously Nucleated Iron(III) (Hydr)oxide on Quartz

Poorly crystalline iron(III) (hydr)oxide nanoparticles are ubiquitous in environmental systems and play a crucial role in controlling the fate and transport of contaminants. Yet, the thermodynamic and kinetic parameters, e.g., the effective interfacial (α^') and apparent activation (E a ) energies, of iron(III) (hydr)oxide nucleation on earth-abundant mineral surfaces have not been determined, which hinders an accurate prediction of iron(III) (hydr)oxide formation and its interactions with other toxic or reactive ions. Here, for the first time, we report experimentally obtained α^' and E a for iron(III) (hydr)oxide nucleation on quartz mineral surfaces, by employing a flow-through, time-resolved grazing incidence small angle X-ray scattering (GISAXS). GISAXS enabled the in situ detection of iron(III) (hydr)oxide nucleation rates under different supersaturations (σ, achieved by varying pH 3.3-3.6) and temperatures (12-35ºC). By quantitative analyses based on classical nucleation theory, α^' was obtained to be 34.6 mJ/m 2 and E a was quantified as 32.8 kJ/mol. The fundamental thermodynamic and kinetic parameters obtained here will advance our fundamental understanding of the surface chemistry and nucleation behavior of iron(III) (hydr)oxides in subsurface and water treatment systems, as well as their effects on the fate and transport of pollutants in natural and engineered water systems. The in situ flow-through GISAXS method can also be adapted to quantify thermodynamic and kinetic parameters at interfaces for many important solid–liquid environmental systems.

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

Integrated Effects of Site Hydrology and Vegetation on Exchange Fluxes and Nutrient Cycling at a Coastal Terrestrial‐Aquatic Interface

Abstract The complex interactions among soil, vegetation, and site hydrologic conditions driven by precipitation and tidal cycles control the biogeochemical transformations and bi‐directional exchange of carbon and nutrients across the terrestrial–aquatic interfaces (TAIs) in coastal regions. This study uses a highly mechanistic model, Advanced Terrestrial Simulator (ATS)‐PFLOTRAN, to explore how these interactions affect exchanges of materials and carbon and nitrogen cycling. We used a transect in the Chesapeake Bay region that spans zones of open water, coastal wetland, transition, and upland forest. We designed several simulation scenarios to parse the effects of the individual controlling factors and the sensitivity of carbon cycling to reaction rate parameters derived from laboratory experiments. Our simulations reveal an active zone for carbon cycling under the transition zones between the wetland and the upland. Evapotranspiration is found to enhance the exchange fluxes between the surface and subsurface domains, resulting in a higher dissolved oxygen concentration in the TAIs. The transport of organic carbon derived from plant leaves and roots provide an additional source of organic carbon needed for the aerobic respiration and denitrification processes in the TAIs. The variability in reaction rate parameters associated with microbial activities is also found to play a dominant role in controlling the heterogeneity and dynamics of the simulated redox conditions. This modeling‐focused exploratory study enabled us to better understand the complex interactions among soil, water and microbes that govern the hydro‐biogeochemical processes at the TAIs, which is an important step toward representing coastal ecosystems in larger‐scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Structure-activity relationship of Pt catalyst on engineered ceria-alumina support for CO oxidation

In heterogeneous catalysis, the promotion of low temperature activity and enhancement of thermal stability simultaneously especially for precious metal catalysts is always highly demanded but very challenging. In this work, we report a novel Pt catalyst on ceria-alumina (CeO 2 /Al 2 O 3 ) support (Pt/CA-T) engineered by a two-step ceria deposition strategy, exhibiting superior thermal stability and low-temperature carbon monoxide (CO) oxidation activity after activation. Pt single sites anchored to engineered CeO 2 edge sites are much more stable than that to CeO 2 (111) surface, and such stable single sites can be transformed into highly active Pt clusters for efficient low-temperature CO oxidation. Active site identification indicates that the CO oxidation activity of different Pt sites follows such sequence: Pt cluster step sites ≈ Pt cluster terrace sites > Pt cluster corner sites $\gg$ Pt single sites on CeO 2 . The excellent low temperature activity of activated Pt/CA-T catalyst for CO oxidation is associated with its abundant Pt cluster step and terrace sites as well as rich Pt-CeO 2 interfaces, which facilitate the adsorption of active CO species and superior oxygen activation/transfer ability. The present study provides new insights into the structure–activity relationship of Pt-CeO 2 -Al 2 O 3 catalyst, which can also guide the preparation of other highly robust supported catalysts for important industrial applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Pin-by-Pin Core Calculation with an NEM-Based Two-Level Hybrid CMFD Algorithm

In the near future, systematic pin-by-pin core calculations are expected to provide a high level of accuracy. These are being developed in pursuit of high-fidelity tools for analyzing the reactor configurations. One such tool that has recently gained significant attention is the pin-by-pin core calculation via local-global iteration using nonlinear acceleration scheme, such as the One-Node CMFD (Coarse-Mesh Finite Difference) nonlinear algorithm. The One-Node CMFD method uses two correction factors to preserve the interface current, in contrast to the one correction term employed by conventional nonlinear iterative methods such as that proposed by Kord. S. Smith. These correction factors are updated with surface flux and net current which are obtained from a high order local problem. With two correction factors, One-Node CMFD can reduce computing time of local FMFD (Fine-Mesh Finite Difference) as it nonlinearly couples the CMFD and FMFD methods in global-local iterations. Nonetheless, very small mesh size is still required and it consequently requires long computing time for high accuracy. As such, a more flexible approach is needed to address this challenge. This paper presents one such possible approach named the hCMFD (Hybrid CMFD) method. In this method, One-Node CMFD is used to solve the global problem, while Two-Node NEM (Nodal Expansion Method) CMFD replaces FMFD as the solver for the local problem. In this paper, two kinds of CMFD methods has been simultaneously implemented for a global-local nonlinear iteration in order to do pin-by-pin heterogeneous reactor calculations. The global problem is solved by a one-node CMFD which uses two correction factors, while the local fixed-source problem is solved by the conventional two-node NEM CMFD which use one correction factor on a surface. From solution of the global eigenvalue problem, incoming partial current is obtained and it is used as boundary condition of the local fixed-source problems. It has been shown that over 99% of the whole calculations can be done in parallel with the new CMFD method for 2-D problems and the algorithm can be easily parallelized by using the OpenMP parallel scheme. The hCMFD method will enable an efficient pin-by-pin reactor analysis since a very efficient parallel calculation is possible with the hCMFD method. In future works, the hCMFD method will be extended to three-dimensional reactor problem. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Fungal organic acid uptake of mineral-derived K is dependent on distance from carbon hotspot

Fungal mineral weathering regulates the bioavailability of inorganic nutrients from mineral surfaces to organic matter and increase the bioavailable fraction of nutrients. Such weathering strategies are classified as biomechanical or biochemical. In the case of fungal uptake of mineral nutrients through biochemical weathering, it is widely hypothesized that uptake of inorganic nutrients occurs through organic acid chelation, but such processes have not been directly visualized. This is in part due to challenges in probing the complex and heterogeneous soil environment. Here, using an epoxy-based, mineral-doped soil micromodel platform, which emulates soil mineralogy and porosity, we visualize the molecular mechanisms of mineral weathering. Mass spectrometry imaging revealed differences in the distribution of fungal exudates, citric acid, and tartaric acid on the soil micromodels in presence of minerals. Citric acid was detected closer to the nutrient-rich inoculation point, whereas tartaric acid was highly abundant away from inoculation point. This suggested that the organic acid exuded by the fungi depended on the proximity from the carbon-rich organic substrate at the point of inoculation. Using a combination of X-ray fluorescence and X-ray near edge structure analysis, we identified citric acid- and tartaric acid-bound K within fungal hyphae networks grown in the presence of minerals. Combined, our results provide direct evidence that fungi uptake and transport mineral derived nutrient organic acid chelation. The results of this study provided unprecedented visualization of fungal uptake and transport of K + , while resolving the indirect weathering mechanism of fungal K uptake from mineral interfaces.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Excited Electron Dynamics at Semiconductor–Molecule Type-II Heterojunction Interface: First-Principles Dynamics Simulation

Excited electron dynamics at semiconductor–molecule interfaces is ubiquitous in various energy conversion technologies. However, a quantitative understanding of how molecular details influence the quantum dynamics of excited electrons remains a great scientific challenge because of the complex interplay of different processes with various time scales. Here in this paper, we employ first-principles electron dynamics simulations to investigate how molecular features govern the dynamics in a representative interface between the hydrogen-terminated Si(111) surface and a cyanidin molecule. Hot electron transfer to the chemisorbed molecule was observed but was short-lived on the molecule. Interfacial electron transfer to the chemisorbed molecule was found to be largely decoupled from hot electron relaxation within the semiconductor surface. While the hot electron relaxation was found to take place on a time scale of several hundred femtoseconds, the subsequent interfacial electron transfer was slower by an order of magnitude. Finally, at the same time, this secondary process of picosecond electron transfer is comparable in time scale to typical electron trapping into defect states in the energy gap.

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

Enhanced Radiation Damage Tolerance of Amorphous Interphase and Grain Boundary Complexions in Cu-Ta

Amorphous interfacial complexions are particularly resistant to radiation damage and have been primarily studied in alloys with good glass-forming ability, yet recent reports suggest that these features can form even in immiscible alloys such as Cu-Ta under irradiation. In this work, the mechanisms of damage production and annihilation due to primary knock-on atom collisions are investigated for amorphous interphase and grain boundaries in a Cu-Ta alloy using atomistic simulations. Amorphous complexions, in particular amorphous interphase complexions that separate Cu and Ta grains, result in less residual defect damage than their ordered counterparts. Stemming from the nanophase chemical separation in this alloy, the amorphous complexions exhibit a highly heterogeneous distribution of atomic excess volume, as compared to a good glass former like Cu-Zr. Complexion thickness, a tunable structural descriptor, plays a vital role in damage resistance. Thicker interfacial films are more damage-tolerant because they alter the defect production rate due to differences in intrinsic displacement threshold energies during the collision cascade. Overall, the findings of this work highlight the importance of interfacial engineering in enhancing the properties of materials operating in radiation-prone environments and the promise of amorphous complexions as particularly radiation damage-tolerant microstructural features.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Scalable simulation of coupled adsorption and transport of methane in confined complex porous media with density preconditioning

The growing significance of shales and tight formations in the transition to less carbon-intensive and clean energy drives the research endeavor to understand the physics of gas flow within these systems. However, shales are composed of massively heterogeneous physical and chemical features. Most nano-sized pores connect to millimeter-scale fractures, leading to multiscale transport. These nano-scale pore throats demonstrate non-classical flow behavior, such as non-negligible slip velocities and adsorbed gas layers at the boundary. As a result, classical computational fluid dynamics models do not capture the physics. In this work, we develop a coupling scheme for the multiple-relaxation-time (MRT) lattice Boltzmann (LB) method that integrates the Peng-Robinson equation of state into a pseudo-potential interaction model to capture the physics of methane flow in irregular networks of channels that represent nano-scale porous media. We use atomistic simulations to calibrate and validate our model in slit nano-channels. We propose a preconditioning scheme to initialize the coupled transport and adsorption simulation of methane in complex porous media. The results of this implementation of LB agree with Direct Simulation Monte Carlo (DSMC) and Molecular Dynamics (MD) simulations. We then scale up the LB implementation through vectorization and indirect addressing. We parallelize it using Message Passing Interface (MPI) and OpenMP frameworks to simulate transport and adsorption in complex media with a million lattices. Additionally, we analyze the differences between coupled and transport-only simulations in two case studies and show that considering phase behavior, i.e., adsorption, can significantly change the flow behavior. This work constitutes an important step towards bridging the gap between molecular flow and system-scale behavior of complex disordered porous media.

42 ENGINEERING↗
DOE OSTI2020

Expression of interfacial Seebeck coefficient through grain boundary engineering with multi-layer graphene nanoplatelets

Energy filtering has been a long-sought strategy to enhance a thermoelectric material's figure of merit zT through improving its power factor. Here we show a composite of multi-layer graphene nanoplatelets (GNP) and n-type Mg 3 Sb 2 leads to the expression of an energy filtering like effect demonstrated by an increase in the material's Seebeck coefficient and maximum power factor, without impact on the material's carrier concentration. We analyse these findings from the perspective of a heterogeneous material consisting of grain and grain boundary phases, instead of a more traditional and common analysis that assumes a homogeneously transporting medium. An important implication of this treatment is that it leads to the development of an interfacial Seebeck coefficient term, which can explain the observed increase in the material's Seebeck coefficient. The contribution of this interfacial Seebeck coefficient to the overall Seebeck coefficient is determined by the relative temperature drop across the grain boundary region compared to that of the bulk material. In Te doped Mg 3 Sb 2 we show the introduction of GNP increases the interfacial thermal resistance of grain boundaries, enhancing the contribution of the interfacial Seebeck coefficient arising from grain boundaries to the overall Seebeck coefficient. Without significant detriment to the electrical conductivity this effect results in a net increase in maximum power factor. This increased interfacial thermal resistance also leads to the synergistic reduction of the total thermal conductivity. As a result, we enhance zT of the Mg 3 Sb 2 to a peak value of 1.7 near 750 K. Considering the two-dimensional nature of the grain boundary interface, this grain boundary engineering strategy could be applied to a few thermoelectric systems utilizing various two-dimensional nanomaterials.

42 ENGINEERING↗
DOE OSTI2018

Role of Thickness Confinement on Relaxations of the Fast Component in a Miscible A/B Blend

Spatial compositional heterogeneity strongly influences the dynamics of the A and B components of bulk miscible blends. Its effects are especially apparent in mixtures, such as poly(vinyl methyl ether) (PVME)/polystyrene (PS), where there exist significant disparities between the component glass transition temperatures (Tgs) and relaxation times. The relaxation processes characterized by distinct temperature dependencies and relaxation rates manifest different local compositional environments for temperatures above and below the glass transition temperature of the miscible blend. This same behavior is shown to exist in miscible PS/PVME films as thin as 100 nm. Moreover, in thin films, the characteristic segmental relaxation times t of the PVME component of miscible PVME/PS blends confined between aluminum (Al) substrates decrease with increasing molecular weight M of the PS component. These relaxation rates are film thickness dependent, in films up to a few hundred nanometers in thickness. This is in remarkable contrast to homopolymer films, where thickness confinement effects are apparent only on length scales on the order of nanometers. These surprisingly large length scales and M dependence are associated with the preferential interfacial enrichment - wetting layer formation - of the PVME component at the external Al interfaces, which alters the local spatial blend composition within the interior of the film. The implications are that the dynamics of miscible thin film blends are dictated in part by component Tg differences, disparities in component relaxation rates, component-substrate interactions, and chain lengths (entropy of mixing).

36 MATERIALS SCIENCE↗
DOE OSTI2019

Initial Steps in Forming the Electrode–Electrolyte Interface: H 2 O Adsorption and Complex Formation on the Ag(111) Surface from Combining Quantum Mechanics Calculations and Ambient Pressure X-ray Photoelectron Spectroscopy

The interaction of water with metal surfaces is at the heart of electrocatalysis. But there remain enormous uncertainties about the atomistic interactions at the electrode-electrolyte interface (EEI). As the first step toward an understanding of the EEI, we report here the details of the initial steps of H 2 O adsorption and complex formation on a Ag(111) surface, based on coupling quantum mechanics (QM) and ambient-pressure X-ray photoelectron spectroscopy (APXPS) experiments. We find a close and direct comparison between simulation and experiment, validated under various isotherm and isobar conditions. We identify five observable oxygen-containing species whose concentrations depend sensitively on temperature and pressure: chemisorbed O* and OH*, H 2 O* stabilized by hydrogen bond interactions with OH* or O*, and multilayer H 2 O*. Furthermore, we identify the species experimentally by their O 1s core-level shift that we calculate with QM along with the structures and free energies as a function of temperature and pressure. This leads to a chemical reaction network (CRN) that we use to predict the time evolution of their concentrations over a wide range of temperature (298-798 K) and pressure conditions (10-6-1 Torr), which agree well with the populations determined from APXPS. This multistep simulation CRN protocol should be useful for other heterogeneous catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Capacitance of Carbon Nanotube/Graphene Composite Electrodes with [BMIM + ][BF$_4^–$]/Acetonitrile: Fixed Voltage Molecular Dynamics Simulations

The capacitance of nanoporous carbon electrode materials is dictated by the physical interactions with electrolyte ions and molecules at the accessible interior electrode surface. While significant progress has been made in designing and synthesizing carbon materials with well-defined and relatively homogeneous nanoporosity, the majority of materials remain heterogeneous, and the resulting properties reflect an average over this distribution. In this regard, computer simulations can be a valuable tool to predict or validate structure/property relationships by systematically investigating well-defined, model electrode morphologies. In this work, we utilize fixed-voltage molecular dynamics simulations to predict structure/capacitance relationships for five different model morphologies of carbon nanotube/graphene (CNT/G) composite electrodes with 1-butyl-3-methylimidazolium tetrafluoroborate/acetonitrile electrolyte. The CNT/G electrode models are inspired by experimental “layer-by-layer” syntheses and strike a balance between realism and computational tractability. Comparison between different model electrode architectures elucidates important structure/property relationships. We find that CNT/graphene contact points serve as “hot spots” with significantly enhanced charge separation relative to the rest of the electrode. Furthermore, we demonstrate a specific nanoconfinement motif that provides substantial 3–4$\times$ enhancement of local capacitance, resulting in a ~40% increase of the total electrode differential capacitance. Because the accessible surface area of the model CNT/G electrodes is precisely determined, a comparison of per-area capacitance across systems is unambiguous. Our results thus complement a prior computational demonstration of capacitance enhancement in nanoconfinement while elucidating additional interaction motifs at CNT/G electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

SU-E-T-355: Efficient Scatter Correction for Direct Ray-Tracing Based Dose Calculation

Purpose: To propose a scatter correction method with linear computational complexity for direct-ray-tracing (DRT) based dose calculation. Due to its speed and simplicity, DRT is widely used as a dose engine in the treatment planning system (TPS) and monitor unit (MU) verification software, where heterogeneity correction is applied by radiological distance scaling. However, such correction only accounts for attenuation but not scatter difference, causing the DRT algorithm less accurate than the model-based algorithms for small field size in heterogeneous media. Methods: Inspired by the convolution formula derived from an exponential kernel as is typically done in the collapsed-cone-convolution-superposition (CCCS) method, we redesigned the ray tracing component as the sum of TERMA scaled by a local deposition factor, which is linear with respect to density, and dose of the previous voxel scaled by a remote deposition factor, D(i)=aρ(i)T(i)+(b+c(ρ(i)-1))D(i-1),where T(i)=e(-αr(i)+β(r(i))2) and r(i)=Σ-(j=1,..,i)ρ(j).The two factors together with TERMA can be expressed in terms of 5 parameters, which are subsequently optimized by curve fitting using digital phantoms for each field size and each beam energy. Results: The proposed algorithm was implemented for the Fluence-Convolution-Broad-Beam (FCBB) dose engine and evaluated using digital slab phantoms and clinical CT data. Compared with the gold standard calculation, dose deviations were improved from 20% to 2% in the low density regions of the slab phantoms for the 1-cm field size, and within 2% for over 95% of the volume with the largest discrepancy at the interface for the clinical lung case. Conclusion: We developed a simple recursive formula for scatter correction for the DRT-based dose calculation with much improved accuracy, especially for small field size, while still keeping calculation to linear complexity. The proposed calculator is fast, yet accurate, which is crucial for dose updating in IMRT optimization.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Facet‐dependent Heterogeneous Fenton Reaction Mechanisms on Hematite Nanoparticles for (Photo)catalytic Degradation of Organic Dyes

Although heterogeneous photo‐Fenton reactions on nanoparticulate iron oxides effectively degrade organic pollutants, the underlying surface mechanisms remain debated. Here, we demonstrate how these pathways are modulated by specific hematite crystal facets. To investigate the influence of particle surface structure, methylene blue (MB) adsorption and photodegradation kinetics are examined using facet‐engineered hematite nanoparticles with distinct exposed facets. The results reveal that MB photodegradation strongly depends on both pH and facet orientation. When normalized by surface area, (116) facet shows higher photodegradation activity than those with (104) or (001) facets. This enhanced activity is attributed to favorable electronic structure and surface characteristics, including a smaller optical bandgap, faster charge transfer, and superior H 2 O 2 decomposition. In contrast, the photodegradation capacity follows (104) 〉 (116) 〉 (001), primarily due to the higher density of surface‐active sites on the (104) facet. These sites promote coupled MB adsorption and degradation, enabling removal of a greater overall quantity of MB. Additionally, under high pH conditions, hematite can degrade MB in the dark, with capacities following (001) ≫ (116) 〉 (104). These findings underscore the critical catalytic role of specific hematite surfaces and advance the understanding of facet‐dependent photoinduced redox chemistry at mineral–water interfaces.

(photo)catalytic degradation↗
DOE OSTI2018

Direct Assessment of Nanoconfined Water in 2D Ti 3 C 2 Electrode Interspaces by a Surface Acoustic Technique

Although significant progress has been achieved in understanding of ion-exchange mechanisms in the new family of 2D transition metal carbides and nitrides known as MXenes, direct gravimetric assessment of water insertion into the MXene interlayer spaces and mesopores has not been reported so far. Concurrently, the latest research on MXene and Birnessite electrodes shows that nanoconfined water dramatically improves their gravimetric capacity and rate capability. Hence, quantification of the amount of confined water in solvated electrodes is becoming an important goal of energy-related research. Using the recently developed and highly sensitive method of in situ hydrodynamic spectroscopy (based on surface-acoustic probing of solvated interfaces), we provide clear evidence that typical cosmotropic cations (Li + , Mg 2+ , and Al 3+ ) are inserted into the MXene interspaces in their partially hydrated form, in contrast to the insertion of chaotropic cations (Cs + and TEA + ), which effectively dehydrate the MXene. These new findings provide important information about the charge-storage mechanisms in layered materials by direct quantification and efficient control (management) over the amount of confined fluid in a variety of solvated battery/supercapacitor electrodes. Here, we believe that the proposed monitoring of water content as a function of the nature of ions can be equally applied to solvated biointerfaces, such as the ion channels of membrane proteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Greenlighting Photoelectrochemical Oxidation of Water by Iron Oxide

Hematite (alpha-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematites modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d) -> Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation.

absorbed photon-to-current conversion efficiency (↗
DOE OSTI2016

Progress in the Analysis of Complex Atmospheric Particles

This manuscript presents an overview on recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surfaces interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multi-modal chemical characterization of particles with both molecular and lateral specificity. When combined, they provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore environmental effects of air-surface interactions.

Aerosol↗
DOE OSTI2019

Organic-Mineral Interfacial Chemistry Drives Heterogeneous Nucleation of Sr-Rich (Bax, Sr1-x)SO4 from Undersaturated Solution

Sr-bearing marine barite [(Bax, Sr1-x)SO4] cycling has been widely used to reconstruct geochemical evolutions of paleoenvironments. However, an understanding of barite precipitation in the ocean, which is globally undersaturated with respect to barite, is missing. Moreover, the reason for the occurrence of higher Sr content in marine barites than expected for classical crystal growth processes remains unknown. Field data analyses suggested that organic molecules may regulate the formation and composition of marine barites; however, the specific organic–mineral interactions are unclear. Using in situ grazing incidence small-angle X-ray scattering (GISAXS), size and total volume evolutions of barite precipitates on organic films were characterized. The results show that barite forms on organic films from undersaturated solutions. Moreover, from a single supersaturated solution with respect to barite, Sr-rich barite nanoparticles formed on organics, while micrometer-size Sr-poor barites formed in bulk solutions. Ion adsorption experiments showed that organic films can enrich cation concentrations in the adjacent solution, thus increasing the local supersaturation and promoting barite nucleation on organic films, even when the bulk solution was undersaturated. The Sr enrichment in barites formed on organic films was found to be controlled by solid-solution nucleation rates; instead, the Sr-poor barite formation in bulk solution was found to be controlled by solid-solution growth rates. This study provides a mechanistic explanation for Sr-rich marine barite formation and offers insights for understanding and controlling the compositions of solid solutions by separately tuning their nucleation and growth rates via the unique chemistry of solution–organic interfaces.

Deng, Ning↗