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At least 721 records · Page 40

Numerical coupling of aerosol emissions, dry removal, and turbulent mixing in the E3SM Atmosphere Model version 1 (EAMv1) – Part 2: A semi-discrete error analysis framework for assessing coupling schemes

Abstract. Part 1 (Wan et al., 2024) of this study discusses the motivation and empirical evaluation of a revision to the aerosol-related numerical process coupling in the atmosphere component of the Energy Exascale Earth System Model version 1 (EAMv1) to address the previously reported issue of strong sensitivity of the simulated dust aerosol lifetime and dry removal rate to the model's vertical resolution. This paper complements that empirical justification of the revised scheme with a mathematical justification leveraging a semi-discrete analysis framework for assessing the splitting error of process coupling methods. The framework distinguishes the error due to numerical splitting from the error due to the time integration method(s) used for each individual process. Such a distinction results in a framework that provides an intuitive understanding of the causes of the splitting error. The application of this framework to the dust life cycle in EAMv1 confirms (i) that the original EAMv1 scheme artificially strengthens the effect of dry removal processes and (ii) that the revised splitting reduces that artificial strengthening. While the error analysis framework is presented in the context of the dust life cycle in EAMv1, the framework can be broadly leveraged to evaluate process coupling schemes, both in other physical problems and for any number of processes. This framework will be particularly powerful when the various process implementations support a variety of time integration approaches. Whereas traditional local truncation error approaches require separate consideration of each combination of time integration methods, this framework enables evaluation of coupling schemes independent of particular time integration approaches for each process while still allowing for the incorporation of these specific time integration errors if so desired. The framework also explains how the splitting error terms result from (i) the integration of individual processes in isolation from other processes and (ii) the choices of input state and time step size for the isolated integration of processes. Such a perspective has the potential for the rapid development of alternative coupling approaches that utilize knowledge both about the desired accuracy and about the computational costs of individual processes.

58 GEOSCIENCES↗

Eastern North Atlantic Aerosol Mask (ENA-AM) with the Condensation Particle Counter (CPC) at Central Facility (C1) during Summer 2017

Eastern North Atlantic (ENA) Aerosol Mask (ENA-AM) is a mask developed to isolate high concentration aerosol events and identify the regional baseline in one minute time resolution CPC measurements collected at ENA central site during summer 2017(July 22 to August 20). ENA-AM is based on the statistically different behavior of adjacent data points during background and pollution peaks measurements. Measurements that differ by more than α times the standard deviation (σm) of the data below the median plus the two points after are masked by ENA-AM.

54 ENVIRONMENTAL SCIENCES↗

Eastern North Atlantic Aerosol Mask (ENA-AM) with the Condensation Particle Counter (CPC) at Central Facility (C1) during Winter 2017

Eastern North Atlantic (ENA) Aerosol Mask (ENA-AM) is a mask developed to isolate high concentration aerosol events and identify the regional baseline in one minute time resolution CPC measurements collected at ENA central site during Winter 2017(December 1-30). ENA-AM is based on the statistically different behavior of adjacent data points during background and pollution peaks measurements. Measurements that differ by more than α times the standard deviation (σm) of the data below the median plus the two points after are masked by ENA-AM.

54 ENVIRONMENTAL SCIENCES↗

Eastern North Atlantic Aerosol Mask (ENA-AM) with the Condensation Particle Counter (CPC) at Supplementary Facility (S01)

Eastern North Atlantic (ENA) Aerosol Mask (ENA-AM) is a mask developed to isolate high concentration aerosol events and identify the regional baseline in one minute time resolution CPC measurements collected at the ENA supplementary site (S1) during summer (July 22 to August 20) 2017. ENA-AM is based on the statistically different behavior of adjacent data points during background and pollution peaks measurements. Measurements that differ by more than α times the standard deviation (σm) of the data below the median plus the two points after are masked by ENA-AM.

54 ENVIRONMENTAL SCIENCES↗

Aerosol samples overview from the AEROICESTUDY campaign

Mastersheet of aerosol samples collected by a Microorifice Uniform Deposit Impactor (MOUDI) during the Aerosol-Ice Formation Closure Pilot Study (AEROICESTUDY) at SGP occurring 7 – 28 October 2019. Dates and times of collection and location/storage and types of samples are described. Please read AEROICESTUDY_MOUDI_README.csv file for details.

54 ENVIRONMENTAL SCIENCES↗

Arctic Black Carbon Aerosol Deposition Study North Slope of Alaska 2020- ACSM Measurements

Particles are removed from the atmosphere through both wet and dry deposition. These processes are poorly understood, though they constitute important uncertainties in climate and air quality models. This project aims to use observational constraints on particle fluxes to improve model representations of dry deposition. In support of black carbon (SP2) and particles (UHSAS) flux measurements at the meteorological tower, we measured non-refractory chemically-speciated aerosol composition with an Aerosol Chemical Speciation Monitor at the the NSA Central Facility (C1). ACSM measurements were made between 9 Sept and 26 Oct 2021. This site is a coastal tundra location, and received snow during the project.

Aerosol Chemical Speciation Monitor↗

Predicting Deposition Rate and Closing the Loop on Aerosol Jet Printing with In‐Line Light Scattering Measurements

Aerosol jet printing is a compelling noncontact, digital manufacturing technology for flexible, hybrid, and conformal electronics, but batch‐to‐batch variability and process drift inhibit systematic study and translation to production environments. Emerging measurement techniques for the aerosol volume fraction, a key parameter governing deposition rate, have shown promise for real‐time response, including a recent demonstration of human‐in‐the‐loop control. By integrating improved light scattering measurements with custom software, a robust environment for real‐time monitoring is established and fully automated closed‐loop control over the deposition rate during printing is enabled. The physical basis for scattering measurements as a feedback source is examined and the quantitative insight this provides for ink development and fundamental process studies is highlighted. Three candidate process variables for closed‐loop control, namely the atomizer voltage, carrier gas flow rate, and print speed, are then evaluated. The atomizer voltage demonstrates the best extended duration validity because it addresses atomization variability directly, but carrier gas flow rate and print speed provide faster and more deterministic responses. This methodology is then demonstrated for electrical properties using a silver nanoparticle ink, maintaining 98% of printed patterns within 10% of the mean resistance value over 3 h of printing.

36 MATERIALS SCIENCE↗

Autonomous Aerosol and Plasma Co‐Jet Printing of Metallic Devices at Ambient Temperature

Abstract Additive manufacturing of metallic materials holds the potential to revolutionize the fabrication of functional devices unattainable via traditional methods. Despite recent advancements, printing metallic materials typically requires thermal processing at elevated temperatures to form dense structures with desired properties, which presents a major challenge for direct printing and integration with temperature‐sensitive materials. Herein, a unique co‐jet printing (CJP) method is reported integrating an aerosol jet and a non‐thermal, atmospheric pressure plasma jet to enable concurrent aerosol deposition of metal nanoparticle inks and in situ sintering at ambient temperature. A machine learning algorithm is integrated with the CJP to perform real‐time defect detection and autonomous correction, enhancing the yield of printed films with high electrical conductivity from 44% to 94%. Concurrent printing and sintering eliminate the need for post‐printing processing, reducing the overall manufacturing time by multiple folds depending on product size. CJP enables direct printing of functional devices on a variety of temperature‐sensitive materials including biological materials. Direct printing of hydration sensors on living plant leaves is demonstrated for long‐duration monitoring of hydration level in the plant. The versatile CJP method opens tremendous opportunities to harmoniously integrate abiotic and biotic materials for emerging applications in wearable/implantable devices and biohybrid systems.

Du, Yipu [Department of Aerospace and Mechanical E↗

All-aerosol-jet-printed highly sensitive and selective polyaniline-based ammonia sensors: a route toward low-cost, low-power gas detection

In this work, we report the design and scalable fabrication of a low-cost and low-power polyaniline-based (PANI) ammonia (NH3) gas sensor on polyimide (PI) substrates using additive manufacturing techniques. The silver interdigitated electrode (IDE) arrays and conducting polymer films are printed onto PI using a direct-write technology of aerosol-jet printing. Morphological characteristics are examined by scanning electron microscopy and energy-dispersive X-ray analysis which reveal homogeneously printed PANI film on the IDE platform. The gas sensing performance is evaluated in the analytical early leak detection range of 5–1000 ppm NH3 in air as a function of both thermal (23 °C, 50 °C, 80 °C) and relative humidity (RH = 0%, 30%, 50%) exposures. The sensor exhibits sensitivity down to 5 ppm NH3 with a sub-ppm detection limit and good repeatability. We observe rapid NH3 detection at 0% RH with very extended times for equilibration and recovery. However, at both 30 and 50% RH, the room temperature response and recovery times are reduced to only about 1 min and 5 min, respectively. Experiments also reveal good sensitivity toward the analyte even at higher operating temperatures. Present results merit the practical application of aerosol-jet-printed, low-power sensors for industrial applications where low-level hazardous gas detection is essential.

36 MATERIALS SCIENCE↗

In-situ qualification and physics-based process design for aerosol jet printing via spatially correlated light scattering measurements

Aerosol jet printing is a contactless, digital, and additive technique broadly used for manufacturing flexible, hybrid, and conformal electronics. However, batch-to-batch variability has hindered widespread industry adoption and scaling to production volumes. Recently, light scattering measurements have emerged as a tool to measure aerosol volume fraction – a key parameter determining deposition rate – and have proven an effective feedback source for closed loop control on timescales ranging from minutes to hours. Here, the efficacy of light scattering measurements as a tool for in-situ qualification over shorter time durations is explored. To be the linear relationship between light scattering measurements and deposition rate was validated at 500 ms time intervals, allowing deposition rate to be mapped to positional coordinates and providing a new data stream to drive quality control assessments. Because light scattering measurements are indicative of a physical process parameter, they were substituted into equations for resistance and sheet resistance, resulting in predictions nominally within 10% of measured values for sets of printed devices. Finally, to highlight a more active utility, light scattering measurements were employed in a print repair framework, successfully repairing prints with randomly induced defects to within 5% of the measured resistance of a control set.

36 MATERIALS SCIENCE↗

Projected network performance for next generation aerosol monitoring systems

Aerosol monitoring for radioactivity is a mature and proven technology. However, by improving key specifications of aerosol monitoring equipment, more samples per day can be collected and analyzed with the same minimum detectable concentrations as current systems. This work models hypothetical releases of 140 Ba and 131 I over a range of magnitudes corresponding to the inventory produced from the fission of about 100 g to 1 kiloton TNT-equivalent of 235 U. The releases occur over an entire year to incorporate the natural variability in atmospheric transport. Sampling equipment located at the 79 locations for radionuclide stations identified in the Comprehensive Nuclear-Test-Ban Treaty (CTBT) for the International Monitoring System are used to determine the detections of the individual releases. Alternative collection schemes in next generation equipment that collect 2, 3, or 4 samples per day, rather than the current 1 sample per day, would result in detections in many more samples at more stations with detections for a given release level. The authors posit that next generation equipment will result in increased network resilience to outages and improved source-location capability for lower yield source releases. The application of dual-detector and coincidence measurements to these systems would significantly boost sensitivity for some isotopes and would further enhance the monitoring capability.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Development and testing of a continuous maritime monitor for radionuclide aerosols

Monitoring airborne concentrations of radionuclide activity may provide a timely warning to sea-based assets to avoid contamination from a radioactive plume. The development and testing of an automated aerosol monitoring system that can capture and detect radioactive particulate from marine air is presented. A custom electrostatic precipitator (ESP) was designed to capture particulate onto a reusable collection media. The collection efficiency of the ESP system for radon progeny was determined to be ~23%. A conservative calculation of the minimum detectable concentration of 214 Bi was estimated as 0.3-8 Bq/m 3 . The system was demonstrated in continuous operation, without consumables and limited maintenance, in a marine environment at the PNNL campus in Sequim, Washington. In conclusion, a successful 2-month deployment indicates the feasibility of the approach for continuous maritime monitoring for radionuclide aerosols.

Moore, Michael E. [Pacific Northwest National Labo↗

Aerosols are critical for “nowcasting” climate

Here, aerosols are a critical part of the earth’s energy balance and are changing rapidly. Monitoring Earth’s energy budget, clouds and aerosols with a coherent observing system from the ground, air and space, coupled with predictive models is necessary for timely, updated climate ‘nowcasts.’

Gettelman, Andrew [Pacific Northwest National Labo↗

Controlled Dy-doping to nickel-rich cathode materials in high temperature aerosol synthesis

Layered nickel-rich materials are promising next-generation cathode materials for lithium ion batteries due to their high capacity and low cost. However, the poor thermal stability and longtime cycling performance hinders the commercial applications of high nickel materials. Doping with heteroatoms has been an effective approach for improving electrochemical performance of cathode materials. Controlling doping concentration and geometrical distribution is desired for optimal electrochemical performance, but it is challenging in traditional co-precipitation methods. In this work, controlled dysprosium (Dy) doping to NCM811 was studied in an aerosol synthesis method by controlling the precursor concentrations and heating parameters. The obtained materials were characterized by SEM, XRD, and XPS, and their electrochemical properties and thermal stability were evaluated. By controlling the doping concentration (1.5%), Dy-doped NCM811 was improved simultaneously in long-term cycling and high-rate performance. Here, the thermal-chemical stability of the Dy-doped cathode materials was examined in a microflow reactor with a mass spectrometer. The results showed that Dy-doping shifted the O 2 onset temperature to a higher temperature and reduced O 2 release by 80%, thus dramatically increasing the thermal-chemical stability and improving the fire safety of cathode materials. Since high temperature aerosol synthesis is a low-cost and scalable method, the findings in this work have broad implications for commercial synthesis of novel materials with controlled doping modification to achieve high electrochemical performance and safety in lithium ion batteries.

25 ENERGY STORAGE↗

Volatility Basis Set Distributions and Viscosity of Organic Aerosol Mixtures: Insights from Chemical Characterization Using Temperature-Programmed Desorption–Direct Analysis in Real-Time High-Resolution Mass Spectrometry

Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosols (OA) mixtures is critical for predicting and comprehending the formation and evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature programmed desorption - direct analysis in real time – high resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of a-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol -1 ) and saturated vapor mass concentrations (C T *, µg∙m -3 ) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, µg∙m -3 ). Further, the VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, enabling their categorization into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant total organic mass loadings (tOM) values of 1–100 µg∙m -3 . Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, C T *, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flash Freeze Flow Tube to Vitrify Aerosol Particles at Fixed Relative Humidity Values

Development of methods to measure the phase transitions and physical properties of submicron atmospheric aerosol particles is needed to better model these systems. Here, we introduce a method to flash freeze submicron particles to measure phase transitions as a function of relative humidity (RH). Particles are equilibrated at a fixed RH, vitrified in a temperature-controlled flow tube, and imaged with cryogenic transmission electron microscopy (cryo-TEM). We demonstrate the use of the technique for measuring the efflorescence relative humidity (ERH) of potassium sulfate and potassium chloride aerosol as well as the separation RH for a multicomponent organic/inorganic system that undergoes liquid-liquid phase separation (LLPS). The location of phase transitions can shift between the micrometer and nanometer size regimes and particles in a given population may have a range of RH over which a phase transition occurs. This technique addresses these requirements by allowing for characterization of the phase transitions for individual particles in a population on the submicron scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupling of Lipid Peroxidation and Criegee Intermediate Mediated Autoxidation in the Heterogeneous Oxidation of Linoleic Acid Aerosols

Autoxidation is an established mechanism for the degradation of organic molecules, which is relevant in the atmosphere, combustion processes, the environment, and the rancidification of lipids (commonly known as lipid peroxidation). Autoxidation proceeds via radical chain reactions involving hydroxyl (•OH), peroxy (RO2•), and alkoxy radicals, which are also prominent oxidants in the atmosphere. Recent reports have provided evidence for an alternative autoxidation mechanism driven instead by Criegee intermediates (CIs), which are produced from the reaction of β-hydroxy peroxy radicals (β-OH-RO2•). This work evaluates the contributions of these two mechanisms in the •OH initiated heterogeneous oxidation of linoleic acid (LA) aerosols. Reaction kinetics and product distributions are monitored using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer. To explain the observed kinetics, a kinetic model is developed that incorporates both the conventional peroxidation and alternative CI-mediated autoxidation mechanisms. We observe that the CI-mediated autoxidation pathways enhance the heterogeneous autoxidation rate, while the peroxidation reactions, although present, contributes less to the overall oxidation rate. α-Acyloxyalkyl hydroperoxides (AAHPs) are identified as key indicators for bimolecular reactions of CI with LA, highlighting the role of LA as a CI scavenger. Moreover, the measured functionalized LA products with hydroxyl or carbonyl group(s), serve as markers for the peroxidation reactions. In summary, this work presents a quantitative framework to understand the coupled reaction network of •OH, RO2•, β-OH-RO2• radicals, and CI in driving heterogeneous autoxidation, which is crucial for understanding degradation mechanisms of organic molecules in the environment and atmosphere.

Criegee intermediate↗