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McFiggans, Gordon

Publications and source records attributed to McFiggans, Gordon.

5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Global organic and inorganic aerosol hygroscopicity and its effect on radiative forcing

The climate effects of atmospheric aerosol particles serving as cloud condensation nuclei (CCN) depend on chemical composition and hygroscopicity, which are highly variable on spatial and temporal scales. Here we present global CCN measurements, covering diverse environments from pristine to highly polluted conditions. We show that the effective aerosol hygroscopicity, κ, can be derived accurately from the fine aerosol mass fractions of organic particulate matter (ϵ org ) and inorganic ions (ϵ inorg ) through a linear combination, κ = ϵ org · κ org + ϵ inorg · κ inorg . In spite of the chemical complexity of organic matter, its hygroscopicity is well captured and represented by a global average value of κ org = 0.12 ± 0.02 with κinorg = 0.63 ± 0.01 as the corresponding value for inorganic ions. By showing that the sensitivity of global climate forcing to changes in κ org and κ inorg is small, we constrain a critically important aspect of global climate modelling.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Simulating organic aerosol in Delhi with WRF-Chem using the volatility-basis-set approach: exploring model uncertainty with a Gaussian process emulator

The nature and origin of organic aerosol in the atmosphere remain unclear. The gas–particle partitioning of semi-volatile organic compounds (SVOCs) that constitute primary organic aerosols (POAs) and the multigenerational chemical aging of SVOCs are particularly poorly understood. The volatility basis set (VBS) approach, implemented in air quality models such as WRF-Chem (Weather Research and Forecasting model with Chemistry), can be a useful tool to describe emissions of POA and its chemical evolution. However, the evaluation of model uncertainty and the optimal model parameterization may be expensive to probe using only WRF-Chem simulations. Gaussian process emulators, trained on simulations from relatively few WRF-Chem simulations, are capable of reproducing model results and estimating the sources of model uncertainty within a defined range of model parameters. In this study, a WRF-Chem VBS parameterization is proposed; we then generate a perturbed parameter ensemble of 111 model runs, perturbing 10 parameters of the WRF-Chem model relating to organic aerosol emissions and the VBS oxidation reactions. This allowed us to cover the model's uncertainty space and to compare outputs from each run to aerosol mass spectrometer observations of organic aerosol concentrations and O:C ratios measured in New Delhi, India. The simulations spanned the organic aerosol concentrations measured with the aerosol mass spectrometer (AMS). However, they also highlighted potential structural errors in the model that may be related to unsuitable diurnal cycles in the emissions and/or failure to adequately represent the dynamics of the planetary boundary layer. While the structural errors prevented us from clearly identifying an optimized VBS approach in WRF-Chem, we were able to apply the emulator in the following two periods: the full period (1–29 May) and a subperiod period of 14:00–16:00 h LT (local time) on 1–29 May. The combination of emulator analysis and model evaluation metrics allowed us to identify plausible parameter combinations for the analyzed periods. We demonstrate that the methodology presented in this study can be used to determine the model uncertainty and to identify the appropriate parameter combination for the VBS approach and hence to provide valuable information to improve our understanding of OA production.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

A method for extracting calibrated volatility information from the FIGAERO-HR-ToF-CIMS and its experimental application

The Filter Inlet for Gases and AEROsols (FIGAERO) is an inlet specificallydesigned to be coupled with the Aerodyne High-Resolution Time-of-FlightChemical Ionization Mass Spectrometer (HR-ToF-CIMS). The FIGAERO-HR-ToF-CIMSprovides simultaneous molecular information relating to both the gas- andparticle-phase samples and has been used to extract vapour pressures (VPs) ofthe compounds desorbing from the filter whilst giving quantitativeconcentrations in the particle phase. However, such extraction of vapourpressures of the measured particle-phase components requires use ofappropriate, well-defined, reference compounds. Vapour pressures for thehomologous series of polyethylene glycols (PEG)((H-(O-CH 2 -CH 2 )n-OH) for n=3 to n=8), covering a rangeof vapour pressures (VP) (10 -1 to 10 -7 Pa) that areatmospherically relevant, have been shown to be reproduced well by a range ofdifferent techniques, including Knudsen Effusion Mass Spectrometry (KEMS).This is the first homologous series of compounds for which a number of vapourpressure measurement techniques have been found to be in agreement,indicating the utility as a calibration standard, providing an ideal set ofbenchmark compounds for accurate characterization of the FIGAERO forextracting vapour pressure of measured compounds in chambers and the realatmosphere. To demonstrate this, single-component and mixture vapour pressuremeasurements are made using two FIGAERO-HR-ToF-CIMS instruments based on anew calibration determined from the PEG series. VP values extracted from bothinstruments agree well with those measured by KEMS and reported values fromliterature, validating this approach for extracting VP data from the FIGAERO.This method is then applied to chamber measurements, and the vapour pressuresof known products are estimated.

47 OTHER INSTRUMENTATION↗
DOE OSTI2017

An efficient approach for treating composition-dependent diffusion within organic particles

Mounting evidence demonstrates that under certain conditions the rate of component partitioning between the gas and particle phase in atmospheric organic aerosol is limited by particle-phase diffusion. To date, however, particle-phase diffusion has not been incorporated into regional atmospheric models. An analytical rather than numerical solution to diffusion through organic particulate matter is desirable because of its comparatively small computational expense in regional models. Current analytical models assume diffusion to be independent of composition and therefore use a constant diffusion coefficient. To realistically model diffusion, however, it should be composition-dependent (e.g. due to the partitioning of components that plasticise, vitrify or solidify). This study assesses the modelling capability of an analytical solution to diffusion corrected to account for composition dependence against a numerical solution. Results show reasonable agreement when the gas-phase saturation ratio of a partitioning component is constant and particle-phase diffusion limits partitioning rate (<10% discrepancy in estimated radius change). However, when the saturation ratio of the partitioning component varies, a generally applicable correction cannot be found, indicating that existing methodologies are incapable of deriving a general solution. Until such time as a general solution is found, caution should be given to sensitivity studies that assume constant diffusivity. Furthermore, the correction was implemented in the polydisperse, multi-process Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) and is used to illustrate how the evolution of number size distribution may be accelerated by condensation of a plasticising component onto viscous organic particles.

54 ENVIRONMENTAL SCIENCES↗