Formation and Aging of Secondary Organic Aerosol from Toluene: Changes in Chemical Composition, Volatility, and Hygroscopicity

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.EPA STAR program RD-835405 Department of Energy Atmospheric Science Research Program (ASR) DESC0007075 NSF Major Research Instrumentation CBET0922643 Wallace Research FoundationChemical Engineerin

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

This is the final version of the article. Available from American Geophysical Union via the DOI in this record.A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.The data presented in the paper will be available through the Bolin Centre database (http://bolin.su.se/data/). The EC H2020 European Research Council ERC (ERC-StGATMOGAIN-278277 and ERC-StG-QAPPA-335478) and integrated project 641816 CRESCENDO Svenska Forskningsrådet Formas (Swedish Research Council Formas) (2015-749), Knut och Alice Wallenbergs Stiftelse (Knut and Alice Wallenberg Foundation Wallenberg Fellowship AtmoRemove), Academy of Finland (grants 272041 and 259005), Natural Environment Research Council (NERC grants NE/M003531/1 and NE/J02175X/1), Norwegian Research Council (EVA grant 229771), Natural Sciences and Engineering Research Council of Canada (NSERC, grant RGPIN/04315-2014), National Science Foundation (NSF, grants ATM-1242258, AGS-1242932, and AGS-1360834), U.S. Environmental Protection Agency (EPA, STAR grant R835410), National Oceanic and Atmospheric Administration (NOAA, CPO award 538NA10OAR4310102), Electric Power Research Institute (EPRI, grant 10004734), U.S. Department of Energy (DOE, grants BER/ASR DE-SC0016559 and DE-SC0012792), Georgia Institute of Technology, and NordForsk (Nordic Centre of Excellence eSTICC) are gratefully acknowledged for funding. The climate model simulations were performed on resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputing Centre. Benjamin Murphy is acknowledged for useful discussions

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources. Plain Language Summary The interaction of airborne particulate matter ("aerosols") with water is of critical importance for processes governing climate, precipitation, and public health. It also modulates the delivery and bioavailability of nutrients to terrestrial and oceanic ecosystems. We present a microphysical explanation to the humidity-dependent water uptake behavior of organic aerosol, which challenges the highly simplified theoretical descriptions used in, e.g., present climate models. With the comprehensive analysis of laboratory data using molecular models, we explain the microphysical behavior of the aerosol over the range of humidity observed in the atmosphere, in a way that has never been done before. We also demonstrate the presence of these phenomena in the ambient atmosphere from data collected in the field. We further show, using two state-of-the-art climate models, that misrepresenting the water affinity of atmospheric organic aerosol can lead to significant biases in the estimates of the anthropogenic influence on climate.Peer reviewe

Experimental Verification of Principal Losses in a Regulatory Particulate Matter Emissions Sampling System for Aircraft Turbine Engines

13-C-AJFF-MST-004This is an open access article under the terms of the Creative Commons Attribution-Noncommercial-No Derivatives License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.To cite this article: D. B. Kittelson, J. Swanson, M. Aldridge, R. A. Giannelli, J. S. Kinsey, J. A. Stevens, D. S. Liscinsky, D. Hagen, C. Leggett, K. Stephens, B. Hoffman, R. Howard, R. W. Frazee, W. Silvis, T. McArthur, P. Lobo, S. Achterberg, M. Trueblood, K. Thomson, L. Wolff, K. Cerully, T. Onasch, R. Miake-Lye, A. Freedman, W. Bachalo & G. Payne (2022) Experimental verification of principal losses in a regulatory particulate matter emissions sampling system for aircraft turbine engines, Aerosol Science and Technology, 56:1, 63-74, DOI: 10.1080/02786826.2021.1971152A sampling system for measuring emissions of nonvolatile particulate matter (nvPM) from aircraft gas turbine engines has been developed to replace the use of smoke number and is used for international regulatory purposes. This sampling system can be up to 35m in length. The sampling system length in addition to the volatile particle remover (VPR) and other sampling system components lead to substantial particle losses, which are a function of the particle size distribution, ranging from 50 to 90% for particle number concentrations and 10-50% for particle mass concentrations. The particle size distribution is dependent on engine technology, operating point, and fuel composition. Any nvPM emissions measurement bias caused by the sampling system will lead to unrepresentative emissions measurements which limit the method as a universal metric. Hence, a method to estimate size dependent sampling system losses using the system parameters and the measured mass and number concentrations was also developed (SAE 2017; SAE 2019). An assessment of the particle losses in two principal components used in ARP6481 (SAE 2019) was conducted during the VAriable Response In Aircraft nvPM Testing (VARIAnT) 2 campaign. Measurements were made on the 25-meter sample line portion of the system using multiple, well characterized particle sizing instruments to obtain the penetration efficiencies. An agreement of +/-15% was obtained between the measured and the ARP6481 method penetrations for the 25-meter sample line portion of the system. Measurements of VPR penetration efficiency were also made to verify its performance for aviation nvPM number. The research also demonstrated the difficulty of making system loss measurements and substantiates the E-31 decision to predict rather than measure system losses

Toward the determination of joint volatility-hygroscopicity distributions: Development and response characterization for single-component aerosol

This work presents the development and characterization of a thermodenuder for the study and interpretation of aerosol volatility. Thermodenuder measurements are further combined with a continuous-flow streamwise thermal gradient CCN counter to obtain the corresponding aerosol hygroscopicity. The thermodenuder response function is characterized with monodisperse aerosol of variable volatility and hygroscopicity. The measurements are then interpreted with a comprehensive instrument model embedded within an optimization framework to retrieve aerosol properties with constrained uncertainty. Special attention is given to the interpretation of the size distribution of the thermodenuded aerosol, deconvoluting the effects of impurities and multiple charging, and to simplifications on the treatment of thermodenuder geometry, temperature, the cooling section, and the effects of curvature and accommodation coefficient on inferred particle volatility. Retrieved vapor pressures are consistent with published literature and shown to be most sensitive to uncertainty in the accommodation coefficient. Copyright © 2014 American Association for Aerosol Research

CCN data interpretation under dynamic operation conditions

We have developed a new numerical model for the non-steady-state operation of the Droplet Measurement Technologies (DMT) Cloud Condensation Nuclei (CCN) counter. The model simulates the Scanning Flow CCN Analysis (SFCA) instrument mode, where a wide supersaturation range is continuously scanned by cycling the flow rate over 20-120 s. Model accuracy is verified using a broad set of data which include ammonium sulfate calibration data (under conditions of low CCN concentration) and airborne measurements where either the instrument pressure was not controlled or where exceptionally high CCN loadings were observed. It is shown here for the first time that small pressure and flow fluctuations can have a disproportionately large effect on the instrument supersaturation due to localized compressive/expansive heating and cooling. The model shows that, for fast scan times, these effects can explain the observed shape of the SFCA supersaturation-flow calibration curve and transients in the outlet droplet sizes. The extent of supersaturation depletion from the presence of CCN during SFCA operation is also examined; we found that depletion effects can be neglected below 4000 cm-3 for CCN number. © American Association for Aerosol Research

Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO_<i>x</i> under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS_c), and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OS_c ranged from −0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA

Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA. © Author(s) 2015

Organic aerosol in the summertime southeastern United States: Components and their link to volatility distribution, oxidation state and hygroscopicity

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100ĝ€°C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58ĝ€±ĝ€13ĝ€kJĝ€mol&minus;1 for the LO-OOA, 89ĝ€±ĝ€10ĝ€kJĝ€mol&minus;1 for the MO-OOA, 55ĝ€±ĝ€11ĝ€kJĝ€mol&minus;1 for the BBOA, and 63ĝ€±ĝ€15ĝ€kJĝ€molĝ'1 for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest Oĝ€ : ĝ€C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties. © Author(s) 2018