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At least 1,315 records · Page 73

Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols

Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically-relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptake by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated by AP-derived SOA is strongly dependent on particle size and composition. IEPOX uptake occurred only when weight fraction of AP-derived SOA dropped below 50 %, effectively limiting IEPOX uptake to larger particles.

Environmental Molecular Sciences Laboratory↗

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3 - and Cr 0.25 Fe 0.75 (OH) 3 -coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregates simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.

54 ENVIRONMENTAL SCIENCES↗

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model

Understanding the kinetics of toxic ion reactions with ferrihydrite is crucial for predicting the dynamic behavior of contaminants in soil environments. In this study, the kinetics of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite were investigated with a combination of laboratory macroscopic experiments, microscopic investigation and mechanistic modeling. The rates of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite, as systematically studied using a stirred-flow method, was highly dependent on the reaction pH and metal concentrations and varied significantly among four metals. Spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) showed, at sub-nano scales, all four metals were distributed within the ferrihydrite particle aggregates homogeneously after adsorption reactions, with no evidence of surface diffusion-controlled processes. Based on experimental results, we developed a unifying kinetics model for both cation and oxyanion adsorption/desorption on ferrihydrite based on the mechanistic-based equilibrium model CD-MUSIC. Overall, the model described the kinetic results well, and we quantitatively demonstrated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites affected the adsorption and desorption rates. Our results provided a unifying quantitative modeling method for the kinetics of both cation and oxyanion adsorption/desorption on iron minerals.

Environmental Molecular Sciences Laboratory↗

Calcium-Facilitated Aggregation and Precipitation of the Uranyl Peroxide Nanocluster U 60 in the Presence of Na-Montmorillonite

The unique and diverse features of uranyl peroxide nanoclusters may contribute to the enhanced mobility of uranium in the environment. This study examines the sorption of the uranyl peroxide nanocluster [UO 2 (O 2 )(OH)] 60 60- (U 60 ) to Na-montmorillonite (SWy-2), plagioclase (anorthite), and quartz (SiO 2 ) as a function of time, U 60 concentration, and mineral concentration. SWy-2 was studied in both its untreated form as well as after two different pretreatments, denoted as partially treated SWy-2 and fully treated SWy-2. U 60 was removed (~99%) from solution in the presence of untreated and partially treated SWy-2. However, U 60 was not removed from suspensions containing anorthite, quartz, or fully treated SWy-2, even after several months. The removal of U 60 from suspensions containing untreated SWy-2 is promoted in part by the exchange of Li + counter-ions, normally weakly associated with U 60 in solution, for Ca 2+ ions naturally present in the clay. In solution, Ca 2+ ions induce the aggregation of nanoclusters, which precipitate on the surface of SWy-2. Ca-rich U 60 aggregates associated with SWy-2 were identified and characterized by scanning electron microscopy with energy dispersive spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. This research enhances our understanding of the molecular-scale processes controlling U 60 behavior at the mineral–water interface.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Trace Element Mass Flow Rates from U.S. Coal Fired Power Plants

Trace elements (TEs) exit coal-fired power plants (CFPPs) via solid, liquid, and gaseous waste streams. Estimating the TE concentrations of these waste streams is essential to selecting pollution controls and estimating emission reduction benefits. Our report presents a generalizable mass balance model for estimating TE mass flow rates in CFPP waste streams and evaluates model accuracy for the U.S. coal fleet given current data constraints. We stochastically estimate, using a bootstrapping approach, the 2015 plant-level mass flow rates of Hg, Se, As, and Cl to solid, liquid, and gas phase waste streams by combining publicly available data for combusted coal TE concentrations with estimates of TE partitioning within installed air pollution control processes. When compared with measured and reported data on TE mass flow rates, this model generally overestimates masses by 30–50%, with larger errors for Hg. The partitioning estimates are consistent for Se, As, and Cl removal from flue gas, but tend to underestimate Hg removal. While our model is suitable for first-order estimates of TE mass flows, future work to enhance model performance should focus on collecting and using new data on TE concentrations in the coal blend, where data quality is the weakest.

01 COAL, LIGNITE, AND PEAT↗

Development and Validation of a Dynamic Response Model for a Cold Flow Circulating Fluidized Bed

A dynamic response model has been created of the Cold Flow Circulating Fluidized Bed at NETL in Morgantown, WV. The model is considered dynamic, as opposed to steady state, because it is used to predict the transient responses of gas and solids flows throughout the unit as process conditions vary. The model was built in ProTrax with Advanced Continuous Simulation Language (ACSL) custom code. Dynamic experiments, varying both gas and solids flows, in the CFB unit have been used to validate the accuracy of the model. The advantage of this model is its utility in predicting gas hold up and solids flow throughout the unit during transitions of process conditions. Accurate predictions of these phenomena are important in process control and optimization. The dynamic experiments used in validating the model include modulations of the system pressure, move air (solids flow), and riser gas velocity with step and sinusoidal changes.

01 COAL, LIGNITE, AND PEAT↗

Molecular Dynamics Simulations of the Adsorption of Phthalate Esters on Smectite Clay Surfaces

The partitioning of organic contaminants between water and solid surfaces is a key process controlling their fate and transport in natural environments. A novel methodology was developed to predict the adsorption of organic contaminants by smectite clay minerals (high specific surface area adsorbents abundant in natural soils) using molecular dynamics (MD) simulations. The methodology models a stack of flexible Ca- montmorillonite lamellae in direct contact with a bulk aqueous reservoir and uses the metadynamics technique to facilitate the exploration of the free energy landscape. The methodology was tested and validated in the case of six phthalate esters, widely used chemical plasticizers with endocrine disrupting properties. Simulation predictions reveal strong phthalate adsorption, especially for the larger and more hydrophobic phthalates. Predicted partition coefficients (K d values) are consistent with collected batch experimental data. Adsorption was observed on both the exterior basal surfaces and within the interlayer nanopore, with phthalate molecules predominately adopting a flat orientation on the clay surface. Intercalation was also detected in complementary X-ray diffraction (XRD) experiments. A strong inverse relationship between extent of adsorption and clay surface charge density was observed, as phthalate molecules preferentially occupied the more hydrophobic uncharged patches on each surface. Detailed analysis of the free energy of adsorption revealed that phthalate affinity for the clay surface results from a small favorable van der Waals contribution and a large favorable entropic contribution. Overall, this research demonstrates the substantial affinity of smectite clays for phthalate esters and establishes a computational methodology capable of predicting the water-clay partition coefficients of organic contaminants, a key parameter in environmental fate and transport models.

36 MATERIALS SCIENCE↗

P-Mart: Interactive Analysis of Ion Abundance Global Proteomics Data

The use of mass-spectrometry-based techniques for global protein profiling of biomedical or environmental experiments has become a major focus in research centered on biomarker discovery; however, one of the most important issues recently highlighted in the new era of omics data generation is the ability to perform analyses in a robust and reproducible manner. This has been hypothesized to be one of the issues hindering the ability of clinical proteomics to successfully identify clinical diagnostic and prognostic biomarkers of disease. P-Mart (https://pmart.labworks.org) is an interactive web-based software environment that enables domain scientists to perform quality-control processing, statistics, and exploration of large-complex proteomics data sets without requiring statistical programming. P-Mart is developed in a manner that allows researchers to perform analyses via a series of modules, explore the results using interactive visualization, and finalize the analyses with a collection of output files documenting all stages of the analysis and a report to allow reproduction of the analysis.

59 BASIC BIOLOGICAL SCIENCES↗

Retaining large and adjustable elastic strains of kilogram-scale Nb nanowires [Better Superconductor by Elastic Strain Engineering: Kilogram-scale Free-Standing Niobium Metal Composite with Large Retained Elastic Strains]

Crystals held at ultrahigh elastic strains and stresses may exhibit exceptional physical and chemical properties. Individual metallic nanowires can sustain ultra-large elastic strains of 4-7%. However, retaining elastic strains of such magnitude in kilogram-scale nanowires is challenging. Here, we find that under active load, ~5.6% elastic strain can be achieved in Nb nanowires in a composite material. Moreover, large tensile (2.8%) and compressive (-2.4%) elastic strains can be retained in kilogram-scale Nb nanowires when the composite is unloaded to a free-standing condition. It is then demonstrated that the retained tensile elastic strains of Nb nanowires significantly increase their superconducting transition temperature and critical magnetic fields, corroborating ab initio calculations based on BCS theory. This free-standing nanocomposite design paradigm opens new avenues for retaining ultra-large elastic strains in great quantities of nanowires and elastic-strain-engineering at industrial scale.

36 MATERIALS SCIENCE↗

Designing MOFs-Derived FeS 2 @Carbon Composites for High-Rate Sodium Ion Storage with Capacitive Contributions

We present that sodium-ion batteries suffer the disadvantages of poor rate performance and cycling stability due to its sluggish sodiation kinetics. A rational design strategy for both materials compositions and structures has been proposed to meet these challenges. Herein, a triple-component composite derived from metal organic frameworks, comprising FeS 2 , nitrogen sulfur co-doped porous carbon, and reduced graphene oxide (FeS 2 @NSC/G), has been successfully synthesized. With the capacities contributions from different sodium storage routes (diffusion-controlled processes and surface capacitive processes) at varies rate conditions, it is aiming to make full use of each component in the electrode composite and their unique porous structures. Expected electrode properties have been achieved and related electrochemical could behaviors have also been investigated. Finally, the strategy would present a promising thought for composites design, which enhance high-rate electrochemical energy storage performances.

25 ENERGY STORAGE↗

Biopolymer-Templated Titania Film Formation for Nanostructured Coatings Revealed by Machine Learning-Supported Time-Resolved Analysis

This study presents a machine learning approach to derive the film formation of biopolymer-templated titania nanostructures during spray deposition, in combination with in situ grazing-incidence small-angle X-ray scattering (GISAXS). A neural network trained on synthetic GISAXS data directly predicts domain-size distributions from experimental two-dimensional scattering patterns, capturing the full kinetics of nanostructure evolution with high temporal resolution. The predictions reveal hierarchical size distributions and periodic growth features, consistent with layer-by-layer spray deposition and validated by complementary scanning electron microscopy (SEM) imaging. Quantitative comparison with conventional parametric GISAXS fits shows good qualitative agreement, with systematic differences explained by domain-shape assumptions and resolved by applying a geometric scaling factor. Simulated SEM-like surfaces derived from neural network outputs reproduce the porous, foam-like nanoscale morphology observed experimentally, reinforcing the method’s credibility. This integrated approach enables real-time, nondestructive, statistically averaged monitoring of bulk nanostructure development in functional coatings, offering a scalable methodology to accelerate the characterization and process control of sustainably manufactured nanostructured titania films for energy-related applications such as photocatalysis and photovoltaics.

Heger, JulianEliah↗

Self-Assembly Driven Microlithography via Near-Infrared Light Activation

Current vat photopolymerization (VP) relies on UV or visible light to start the rapid crosslinking of liquid photocurable resins into 3D-printed structures. Here, we develop a self-assembly-driven photopatterning approach to photothermally generate polymeric solids by combining thermoplasmonic nanoparticles and thermoresponsive polymers, in which near-infrared (NIR) light activates thermoplasmonic heating of nanoparticles, triggering the irreversible self-assembly of thermoresponsive polymers into insoluble mesoglobules. A small amount of thermal initiator and crosslinker leads to irreversible self-assembly of polymer nanocomposites. NIR light offers deeper penetration and reduced scattering compared to UV, enabling more uniform curing of thicker or filled materials and expanded process control for composites or opaque systems. Thermoplasmonic heat generation is achieved using surface-modified gold nanorods (AuNRs) with a longitudinal localized surface plasmon resonance peak in the NIR region. Key variables such as polymer composition, molecular weight, physical interactions at the nanoparticle–polymer interface, which can be tuned by surface functionalization, AuNR concentration, and pH can be used to tailor the assembly behavior of these systems, including photothermal effect, flocculation, and cloud point temperature, and the mechanical properties of the final structures. Collectively, these results highlight a platform for photothermally-driven microlithography of polymer solids with diverse, tunable macroscopic properties, enabled by low-energy NIR light-activated self-assembly.

36 MATERIALS SCIENCE↗

Electrochemical Nutrient Recovery for the Food–Energy–Water Nexus at Municipal Wastewater Facilities: Multivariate Analyses of Seasonal Sampling and Reactor Performance

Digester-equipped municipal wastewater facilities generate recycle streams with high nutrient loads that increase energy consumption and can cause environmental pollution. The reduction of these loads through electrochemical nutrient recovery (ENR) could enhance the food–energy–water nexus by producing fertilizer (struvite). This study investigated the recovery process through a 1 year sampling of recycle streams and the implementation of nutrient recovery. Time series analyses showed that P (as orthophosphate) concentration was time-variant in digester effluent streams, while N (as ammonia) concentration was time-variant in only the aerobic system. Furthermore, these two nutrient concentrations did not correlate in any of the recycle streams. Subsequent multivariate screening analyses identified anode type, NH 4 + concentration, cathodic potential, P concentration, and temperature as most significant for ENR. Finally, the optimum conditions of cathodic potential, anode area-to-volume ratio, and temperature applied to a real recycle stream resulted in 95% P recovery with 0.03 kWh/kg P. This energy consumption is significantly lower than process energy for conventional P fertilizers (1.1 kWh/kg P) and chemical recovery processes at scale (1.7–12.9 kWh/kg P). Overall, this study recommended specific process controls for nutrient recovery, expanded the variables evaluated for ENR, and demonstrated the ability to significantly impact energy demand associated with P-based fertilizers.

36 MATERIALS SCIENCE↗

Real-Time KMC Simulation of Vacancy-Mediated Intermixing in Au@Ag Octahedral Core–Cubic Shell Nanocrystals with Ab Initio-Guided Kinetics

Utilization of core–shell rather than monometallic nanocrystals (NCs) facilitates fine-tuning of NC properties for applications. However, compositional evolution via intermixing can degrade these properties prompting recent experimental studies. We develop an atomistic-level stochastic model for vacancy-mediated intermixing exploiting a formalism which allows incorporation at an ab initio density functional theory level of not just the thermodynamics of vacancy formation, but also relevant diffusion barriers for a vast number of possible local environments (in the core and in the shell, at the interface, and in the intermixed phase). This facilitates a predictive treatment and comprehensive understanding of intermixing on the relevant time scale (e.g., 10 1 –10 3 s). In contrast, previous modeling at the atomistic level utilized only unrealistic generic prescriptions of barriers or employed simplified continuum treatments. For Au@Ag octahedral core–cubic shell NCs, our modeling not only captures the experimentally observed rate or time scale for intermixing of ~100 s at 450 °C for 60 nm NCs, but also elucidates the underlying rate controlling processes and the effective intermixing barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a UiO-Type Thin Film Electrocatalysis Platform with Redox-Active Linkers

Metal-organic frameworks (MOFs) as electro- catalysis scaffolds are appealing due to the large concentration of catalytic units that can be assembled in three dimensions. To harness the full potential of these materials, charge transport to the redox catalysts within the MOF has to be ensured. Here in this paper, we report the first electroactive MOF with the UiO/PIZOF topology (Zr(dcphOH-NDI)), i.e., one of the most widely used MOFs for catalyst incorporation, by using redox-active naphthalene diimide-based linkers (dcphOH-NDI). Hydroxyl groups were included on the dcphOH-NDI linker to facilitate proton transport through the material. Potentiometric titrations of Zr(dcphOH-NDI) show the proton-responsive behavior via the -OH groups on the linkers and the bridging Zr-μ 3 -OH of the secondary building units with pK a values of 6.10 and 3.45, respectively. When grown directly onto transparent conductive fluorine-doped tin oxide (FTO), 1 μm thin films of Zr(dcphOH-NDI)@FTO could be achieved. Zr(dcphOH-NDI)@FTO displays reversible electrochromic behavior as a result of the sequential one-electron reductions of the redox-active NDI linkers. Importantly, 97% of the NDI sites are electrochemically active at applied potentials. Charge propagation through the thin film proceeds through a linker-to-linker hopping mechanism that is charge-balanced by electrolyte transport, giving rise to cyclic voltammograms of the thin films that show characteristics of a diffusion-controlled process. The equivalent diffusion coefficient, D e , that contains contributions from both phenomena was measured directly by UV/vis spectroelectrochemistry. Using KPF 6 as electrolyte, De was determined to be D e (KPF 6 ) = (5.4 ± 1.1) × 10 -11 cm 2 s -1 , while an increase in countercation size to n-Bu 4 N + led to a significant decrease of D e by about 1 order of magnitude (D e (n-Bu 4 NPF 6 ) = (4.0 ± 2.5) × 10 -12 cm 2 s -1 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multispecies diffusion models: A study of uranyl species diffusion

Rigorous numerical description of multi-species diffusion requires coupling of species, charge, and aqueous and surface complexation reactions that collectively affect diffusive fluxes. The applicability of a fully coupled diffusion model is, however, often constrained by the availability of species self-diffusion coefficients, as well as by computational complication for imposing charge conservation. In this study, several diffusion models with variable complexity in charge and species coupling were formulated and compared to describe reactive multi-species diffusion in groundwater. Diffusion of uranyl [U(VI)] species was used as an example in demonstrating the effectiveness of the models in describing multi-species diffusion. Numerical simulations found that a diffusion model with a single, common diffusion coefficient for all species was sufficient to describe multi-species U(VI) diffusion under steady-state condition of major chemical composition, but not under transient chemical conditions. Simulations revealed that a fully coupled diffusion model can be well approximated by a component-based diffusion model, which considers difference in diffusion coefficients between chemical components, but not between the species within each chemical component. This treatment significantly enhanced computational efficiency at the expense of minor charge conservation. The charge balance in the component-based diffusion model can be rigorously enforced, if necessary, by adding an artificial kinetic reaction term induced by the charge separation. The diffusion models were applied to describe U(VI) diffusive mass transfer in intragranular domains in two sediments collected from US Department of Energy's Hanford 300A where intragrain diffusion is a rate-limiting process controlling U(VI) adsorption and desorption. The grain-scale reactive diffusion model was able to describe U(VI) adsorption/desorption kinetics that has been described using a semi-empirical, multi-rate model. Compared with the multi-rate model, the diffusion models have the advantage to provide spatiotemporal speciation evolution within the diffusion domains.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A Small Temperate Lake in the 21st Century: Dynamics of Water Temperature, Ice Phenology, Dissolved Oxygen, and Chlorophyll a

It is unclear how small temperate lakes will evolve physically and biologically in the whole water column under future climate because previous modeling studies usually focused on only one or two physical or biological state variables in the surface waters. To fill this gap, we used a well-validated lake biogeochemistry model driven with different climate scenarios to predict the dynamics of ice phenology, water temperature, dissolved oxygen (DO) and chlorophyll in a small Canadian temperate lake during the 21st century, considering the influence of catchment hydrology. We find that the ice season and ice thickness of the lake would shrink substantially, resulting in a positive energy feedback between climate and the lake. Due to the reduced heat diffusion and water mixing, the dynamics of water temperature in surface waters and deep waters are considerably different, with surface waters warmed dramatically but deep waters muted to warming. The lake DO concentrations would be depleted by warming in the whole column but the controlling processes are depth dependent. The chlorophyll concentration in the lake is inertia to climate change, mainly due to the mismatch of the timings of peak solar radiation and thermal and nutrient optima. Our analysis indicates that the influence of catchment hydrology is large on the dynamics of DO, but not on other state variables we have examined. Finally, this study suggests that small temperate lakes could be sensitive to climate change but their physical and biological responses could be diverse.

54 ENVIRONMENTAL SCIENCES↗

Soil Organic Matter Temperature Sensitivity Cannot be Directly Inferred From Spatial Gradients

Developing and testing decadal-scale predictions of soil response to climate change is difficult because there are few long-term warming experiments or other direct observations of temperature response. As a result, spatial variation in temperature is often used to characterize the influence of temperature on soil organic carbon (SOC) stocks under current and warmer temperatures. This approach assumes that the decadal-scale response of SOC to warming is similar to the relationship between temperature and SOC stocks across sites that are at quasi steady state; however, this assumption is poorly tested. We developed four variants of a Reaction-network-based model of soil organic matter and microbes using measured SOC stocks from a 4,000-km latitudinal transect. Each variant reflects different assumptions about the temperature sensitivities of microbial activity and mineral sorption. All four model variants predicted the same response of SOC to temperature at steady state, but different projections of transient warming responses. The relative importance of Q max , mean annual temperature, and net primary production, assessed using a machine-learning algorithm, changed depending on warming duration. When mineral sorption was temperature sensitive, the predicted average change in SOC after 100 years of 5 °C warming was –18% if warming decreased sorption or +9% if warming increased sorption. When microbial activity was temperature sensitive but mineral sorption was not, average site-level SOC loss was 5%. Here, we conclude that spatial climate gradients of SOC stocks are insufficient to constrain the transient response; measurements that distinguish process controls and/or observations from long-term warming experiments, especially mineral fractions, are needed.

54 ENVIRONMENTAL SCIENCES↗