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Shilling, John E.

Publications and source records attributed to Shilling, John E..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Kinetic Modeling of Secondary Organic Aerosol in a Weather-Chemistry Model: Parameterizations, Processes, and Predictions for GOAmazon

Secondary organic aerosol (SOA) forms and evolves in the atmosphere through many pathways and processes, over diverse spatial and time scales. Hence, there is a need to represent these widely-varying kinetic processes in large-scale atmospheric models to allow for accurate predictions of the abundance, properties, and impacts of SOA. In this work, we integrated a kinetic, process-level model (simpleSOM-MOSAIC) into a weather-chemistry model (WRF-Chem) to simulate the oxidation chemistry and microphysics of atmospheric SOA. simpleSOM-MOSAIC simulates multigenerational gas-phase chemistry, autoxidation reactions, heterogeneous oxidation, oligomerization, and phase-state-influenced gas/particle partitioning of SOA. As a case study, the integrated WRF-Chem-simpleSOM-MOSAIC (WC-SSM) model was used to simulate the photochemical evolution downwind of a large city (Manaus, Brazil) in the Amazon and, in turn, study the anthropogenic and biogenic interactions in an otherwise pristine environment. Consistent with previous work, we found that OA was enhanced by up to a factor of four in the urban plume due to elevated hydroxyl radical (OH) concentrations, relative to the background, and that this OA was dominated by SOA from biogenic precursors (80%). Further, in addition to accurately simulating the OA enhancement in the urban plume, the model reproduced the magnitude of the OA oxygen-to-carbon (O:C) ratio and broadly tracked the evolution of the aerosol size distribution. Our work highlights the importance of including an integrated, kinetic representation of SOA processes in an atmospheric model

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Atmospheric Radiation Measurement (ARM) airborne field campaign data products between 2013 and 2018

Airborne measurements are pivotal for providing detailed, spatiotemporally resolved information about atmospheric parameters and aerosol and cloud properties, thereby enhancing our understanding of dynamic atmospheric processes. For 30 years, the US Department of Energy (DOE) Office of Science supported an instrumented Gulfstream 1 (G-1) aircraft for atmospheric field campaigns. Data from the final decade of G-1 operations were archived by the Atmospheric Radiation Measurement (ARM) Data Center and made publicly available at no cost to all registered users. To ensure a consistent data format and to improve the accessibility of the ARM airborne data, an integrated dataset was recently developed covering the final 6 years of G-1 operations (2013 to 2018, https://doi.org/10.5439/1999133; Mei and Gaustad, 2024). The integrated dataset includes data collected from 236 flights (766.4 h), which covered the Arctic, the US Southern Great Plains (SGP), the US West Coast, the eastern North Atlantic (ENA), the Amazon Basin in Brazil, and the Sierras de Córdoba range in Argentina. These comprehensive data streams provide much-needed insight into spatiotemporal variability in the thermodynamic quantities and aerosol and cloud properties for addressing essential science questions in Earth system process studies. This paper describes the DOE ARM merged G-1 datasets, including information on the acquisition, data collection challenges and future potentials, and quality control processes. It further illustrates the usage of this merged dataset to evaluate the Energy Exascale Earth System Model (E3SM) with the Earth System Model Aerosol–Cloud Diagnostics (ESMAC Diags) package.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Anthropogenic extremely low volatility organics (ELVOCs) Govern the Growth of Molecular Clusters over the Southern Great Plains during the Springtime

New particle formation (NPF) and growth govern cloud condensation nuclei (CCN) concentrations in many regions. The mechanisms governing the nucleation of molecular clusters vary substantially in different regions of the atmosphere. Additionally, the growth of these clusters from ~2 to 20 nm sizes is often governed by the availability of extremely low volatility organic vapours (ELVOCs). While the pathways to ELVOC formation from the oxidation of biogenic monoterpenes with ozone is better understood, the chemical and mechanistic pathways for ELVOC formation from oxidation of anthropogenic organics are not well understood. We integrate measurements and three-dimensional regional model simulations with the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to understand the processes governing new particle formation and growth and secondary organic aerosol (SOA) formation during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) field campaign at the Southern Great Plains (SGP) observatory in Oklahoma, and contrast it with a site within the Bankhead National Forest (BNF), Alabama in Southeast USA, where 5-year long measurements will begin in 2024. Simulations show that nucleation rates are at least an order of magnitude higher at SGP compared to BNF during the springtime days (April 28 and May 14, 2016), largely due to lower H2SO4 concentrations at BNF, which are needed for nucleation. In addition, the larger CS at BNF (compared to SGP) increase the loss of molecular clusters by coagulation to pre-existing particles. Among the 8 different nucleation mechanisms in WRF-Chem, we find that the amine+H2SO4 nucleation mechanism dominates at the SGP site, while the pure organic ion induced nucleation mechanism dominates over BNF. Through various WRF-Chem sensitivity simulations, we find that anthropogenic ELVOCs are critical for explaining the growth of newly formed particles and the resulting number size distribution observed near the surface at the SGP site during the daytime. In addition, we show that treating organic particles as semisolid, with strong diffusion-limited uptake of organic vapours, brings model predictions into closer agreement with the observed evolution of particle size distribution. Simulations also predict that anthropogenic SOA, formed by the oxidation of aromatic volatile organic compounds (VOCs), is the dominant organic aerosol component at SGP, while biogenic SOA dominates particle composition at the BNF site in Southeast USA on these days.

Shrivastava, ManishKumar B.↗
DOE OSTI2024

Cloud Condensation Nuclei Hygroscopicity Value-Added Product Report

The purpose of the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s Cloud Condensation Nuclei Hygroscopicity Parameter (AOSCCNSMPSKAPPA and AOSCCNUHSASKAPPA) Value-Added Product (VAP) is to calculate the hygroscopicity parameter, kappa, to quantify the ability of aerosols to activate into cloud water droplets. The hygroscopicity parameter is often used to model the cloud condensation nuclei (CCN) activity of atmospheric aerosols of different sizes and compositions, providing additional insight on the influence of aerosols on climate. The AOSCCNUHSASKAPPA VAP was recently developed to provides kappa data for ARM sites where AOSCCNSMPSKAPPA was missing. Laboratory experiments show that the kappa values for highly hygroscopic aerosols vary from 0.5 to 1.4 (Petters and Kreidenweis 2007). For organic compounds they are observed to vary between 0.01 and 0.5. For non-hygroscopic aerosols, such as soot, kappa values are very close to zero. Ambient aerosols are complex mixtures of organic and inorganic compounds and previous observations indicate that kappa values for these aerosols typically vary from 0.05 to 0.9 (Petters and Kreidenweis 2007).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Scanning Mobility Particle Sizer (SMPS)-Aerodynamic Particle Sizer (APS) Merged Size Distribution (mergedsmpsaps) Value-Added Product Report

Aerosol particles influence the Earth’s radiation balance directly by absorbing and scattering light and indirectly by influencing cloud formation, properties, and lifetimes. Measurements of aerosol particle optical properties, mass loading, size distributions, microphysical properties, cloud formation properties, and chemical composition are important for understanding the aerosol life cycle and for validating earth system models that predict these quantities. The Atmospheric Radiation Measurement (ARM) user facility’s Aerosol Observing System (AOS) is a highly instrumented platform designed to house instruments that measure many of these aerosol properties in situ. Currently, ARM operates at least four different instruments that measure a portion of the ambient aerosol size distribution. Most users are interested in the entire size distribution or a portion of the size distribution that extends across the measurement range of multiple instruments. However, merging these distributions is not trivial as the instruments employ different measurement principals and, in most cases, report data as a function of different representations of the aerosol diameter.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Cloud Condensation Nuclei Hygroscopicity Value-Added Product Report

The purpose of the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s Cloud Condensation Nuclei Hygroscopicity Parameter (AOSCCNSMPSKAPPA and AOSCCNUHSASKAPPA) Value-Added Product (VAP) is to calculate the hygroscopicity parameter, kappa, to quantify the ability of aerosols to activate into cloud water droplets. The hygroscopicity parameter is often used to model the cloud condensation nuclei (CCN) activity of atmospheric aerosols of different sizes and compositions, providing additional insight on the influence of aerosols on climate. The AOSCCNUHSASKAPPA VAP was recently developed to provides kappa data for ARM sites where AOSCCNSMPSKAPPA was missing.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Nonequilibrium Behavior in Isoprene Secondary Organic Aerosol

Recent studies have shown that instantaneous gas-particle equilibrium partitioning assumptions fail to predict SOA formation, even at high relative humidity (~85%), and photochemical aging seems to be one driving factor. In this study, we probe the minimum aging time scale required to observe nonequilibrium partitioning of semivolatile organic compounds (SVOCs) between the gas and aerosol phase at ~50% RH. Seed isoprene SOA is generated by photo-oxidation in the presence of effloresced ammonium sulfate seeds at <1 ppbv NO x , aged photochemically or in the dark for 0.3–6 h, and subsequently exposed to fresh isoprene SVOCs. Our results show that the equilibrium partitioning assumption is accurate for fresh isoprene SOA but breaks down after isoprene SOA has been aged for as short as 20 min even in the dark. Modeling results show that a semisolid SOA phase state is necessary to reproduce the observed particle size distribution evolution. The observed nonequilibrium partitioning behavior and inferred semisolid phase state are corroborated by offline mass spectrometric analysis on the bulk aerosol particles showing the formation of organosulfates and oligomers. Here, the unexpected short time scale for the phase transition within isoprene SOA has important implications for the growth of atmospheric ultrafine particles to climate-relevant sizes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Cloud Condensation Nuclei Closure Study Using Airborne Measurements Over the Southern Great Plains

Abstract Airborne measurements of non‐refractory bulk aerosol chemical composition, aerosol size distributions, and cloud condensation nuclei (CCN) were conducted onboard a research aircraft during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems field campaign in the spring and summer of 2016. A CCN closure study for the entire campaign period was performed where measured CCN concentrations at 0.24% and 0.46% supersaturation were compared with the predicted CCN concentrations calculated using κ ‐Köhler theory, three different assumptions of aerosol mixing state, and various assumptions about hygroscopicity, density, and the insoluble fraction of organic particles. We found that the Closure Ratio (CR), calculated as the ratio of predicted to measured CCN concentrations, was equal to one under two different aerosol mixing state assumptions: (a) all particles are composed of 100% organic particles, and (b) particles are externally mixed and composed of pure sulfates, nitrates, and organic particles assuming hygroscopicity values for organic particles ( ) between 0.04 and 0.17. The use of internal mixing state assumption often led to overprediction of CCN concentrations but the agreement within ±20% with the measured CCN concentrations was observed under certain closure permutations. A similar agreement, that is, within ±20%, was also observed using permuted parameters concerning density (1 and 1.5 g cm −3 ) and an insoluble fraction (0% and 20%) of organic particles. These findings may provide constraints on to predict CCN concentrations at a remote continental Southern Great Plains site.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Optical modeling of a radioisotope atmospheric chamber

Abstract Volatile radioisotopes represent a substantial health risk when released into the environment. To better understand the environmental fate of radioisotopes, the authors constructed a cylindrical steel-walled chamber to simulate the atmospheric processing of volatile radioactive gases. Optical modeling was performed for the properties of simulated sunlight in the chamber to better characterize atmospheric reaction studies. Optical simulations were performed using two wall materials (steel and thin-film silica) and validated against experimental measurements. This optical analysis methodology can be used to improve the fidelity of atmospheric models by accounting for optical inhomogeneities enabling a firmer grasp of radioisotopes’ environmental fate. Graphical abstract

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Look Up: Probing the Vertical Profile of New Particle Formation and Growth in the Planetary Boundary Layer With Models and Observations

Abstract The processes of new particle formation (NPF) and growth are important contributors to cloud condensation nuclei (CCN) concentrations, and CCN are important for climate from their impact on planetary radiative forcing. While the general ubiquity and importance of NPF is understood, the vertical extent and governing mechanisms of NPF and growth in the lower troposphere are uncertain. We present an analysis of four NPF events and two non‐NPF events during the HI‐SCALE field campaign at the Southern Great Plains observatory in Oklahoma, USA. First, we analyzed airborne and ground‐based observations of aerosol and gas‐phase properties. Second, we used a column aerosol chemistry and microphysics model to probe factors that influence the vertical profile of NPF. During HI‐SCALE, we found several instances of enhanced NPF occurring several hundred meters above the surface; however, the spatio‐temporal characteristics of the observed NPF made comparisons between airborne‐ and ground‐based observations difficult. The model represented the observed NPF (or lack of NPF) and particle growth at the surface to final diameters within 10 nm. The model predicted enhanced NPF rates in the upper mixed layer, and this enhancement is primarily due to the temperature dependence in the NPF schemes, but this was also dependent on the vertical profile of gas‐phase precursors measured during HI‐SCALE. We found vertical mixing in the model either enhanced or suppressed NPF rates, aerosol number concentrations, and particle growth rates at the surface. Finally, our analysis provides insights for future field campaigns and modeling efforts investigating the vertical profile of NPF.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Formation Process of Particles and Cloud Condensation Nuclei Over the Amazon Rainforest: The Role of Local and Remote New-Particle Formation

Understanding the formation processes of particles and cloud condensation nuclei (CCN) in pristine environments is a major challenge in accurately assessing anthropogenic radiative forcing. Here, using a state-of-the-art model that systematically simulates the chemical processes controlling new-particle formation (NPF) and multi-scale chemical transport, we find that NPF contributes ~90% of the particle number and ~80% of the CCN at 0.5% supersaturation (CCN0.5%) in the pristine Amazon boundary layer during the wet season. The corresponding contributions are only ~30% and ~20% during the dry season because of prevalent biomass burning. In both seasons, about half of the NPF-induced particles and ~85% of the NPF-induced CCN0.5% in the boundary layer originate from the long-range transport of new particles formed hundreds to thousands of kilometers away. Moreover, about 50–65% of the NPF-induced particles and 35–50% of the NPF induced CCN0.5% originate from the downward transport of new particles formed in the free troposphere.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry

Ammonia (NH 3 ) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere-surface exchange of nitrogen. It is recognized as a major source of aerosol pollution, and it may limit the formation of cloud nuclei in remote or cold parts of the atmosphere. For soil and plants, NH 3 -mediated nitrogen can act as a harmful pollutant or as a desirable nutrient, mostly in natural and agricultural settings, respectively. Agriculture is also the main source of atmospheric NH 3 via volatilization from fertilizers and manure processing in livestock farming. The accurate determination of NH 3 emission rates remains a challenge, partly due to the propensity of NH 3 to interact with instrument surfaces leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH 3 , using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample-surface interactions and achieved a 1-σ precision of 10–20 pptv and an immediate 1/e response rate < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method’s capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to 10s of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH 3 h –1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH 3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH 3 emissions from surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ~300 m above ground. We derived NH 3 fluxes between –4 and 18 mol km –2 h –1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH 3 area emissions inventory provided by the US Environmental Protection Agency indicated overall agreement, but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in-situ measurements of ambient NH 3 mixing ratios, and even allow for the airborne mapping of the air-surface exchange of NH 3 .

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NO x , and VOC Precursors

We report monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth, and thus have influences on climate feedbacks. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on H 2 O 2 concentration, which is a proxy for HO 2 concentration. The high O/C ratios observed in the a-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NO x photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, non-linear dependence on input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formation in models.

54 ENVIRONMENTAL SCIENCES↗