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The indoor surfaces of dwellings across the United States range exhibit a wide range of chemical compositions and physical properties, which impacts semi-volatile partitioning, heterogeneous chemistry and the overall properties of indoor air. 

ABSTRACT: At fixed aerosol acidity, we recently demonstrated that dimers in isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) can heterogeneously react with hydroxyl radical (·OH) at faster rates than monomers. Aerosol acidity influences this aging process by enhancing the formation of oligomers in freshly generated IEPOX-SOA. Therefore, we systematically examined the role of aerosol acidity on kinetics and products resulting from heterogeneous ·OH oxidation of freshly generated IEPOX-SOA. IEPOX reacted with inorganic sulfate aerosol of varying initial pH (0.5, 1.5, and 2.5) in a steady state smog chamber to yield a constant source of freshly generated IEPOX-SOA, which was aged in an oxidation flow reactor for 0−22 equiv days of atmospheric ·OH exposure. Molecular-level chemical analyses revealed that the most acidic sulfate aerosol (pH 0.5) formed the largest oligomeric mass fraction, causing the slowest IEPOX-SOA mass decay with aging. Reactive uptake coefficients of ·OH (γOH) were 0.24 ± 0.06, 0.40 ± 0.05, and 0.49 ± 0.20 for IEPOX-SOA generated at pH 0.5, 1.5, and 2.5, respectively. IEPOXSOA became more liquid-like for pH 1.5 and 2.5, while exhibiting an irregular pattern for pH 0.5 with aging. Using kinetic and physicochemical data derived for a single aerosol pH in atmospheric models could inaccurately predict the fate of the IEPOX-SOA. 

ABSTRACT: Isoprene has the highest atmospheric emissions of any nonmethane hydrocarbon, and isoprene epoxydiols (IEPOX) are well-established oxidation products and the primary contributors forming isoprene-derived secondary organic aerosol (SOA). Highly acidic particles (pH 0−3) widespread across the lower troposphere enable acid-driven multiphase chemistry of IEPOX, such as epoxide ring-opening reactions forming methyltetrol sulfates through nucleophilic attack of sulfate (SO4 2−). Herein, we systematically demonstrate an unexpected decrease in SOA formation from IEPOX on highly acidic particles (pH < 1). While IEPOX-SOA formation is commonly assumed to increase at low pH when more [H+] is available to protonate epoxides, we observe maximum SOA formation at pH 1 and less SOA formation at pH 0.0 and 0.4. This is attributed to limited availability of SO4 2− at pH values below the acid dissociation constant (pKa) of SO42− and bisulfate (HSO4−). The nucleophilicity of HSO4− is 100× lower than SO42−, decreasing SOA formation and shifting particulate products from low-volatility organosulfates to higher-volatility polyols. Current model parameterizations predicting SOA yields for IEPOX-SOA do not properly account for the SO42−/HSO4 − equilibrium, leading to overpredictions of SOA formation at low pH. Accounting for this underexplored acidity-dependent behavior is critical for accurately predicting SOA concentrations and resolving SOA impacts on air quality. 

Abstract Number: 381 Working Group: Instrumentation and Methods Abstract The phase state of atmospheric aerosol particles – solid, semi-solid, or liquid – influences their ability to take up water and participate in heterogeneous chemical reactions. Changes in phase state have been predicted by glass transition temperature (Tg) and viscosity; however, direct measurements of these properties is challenging for sub-micron particles. Historically, bulk measurements have been used, but this does not account for particle-to-particle variation or the impacts of particle size. Melting temperature (Tm) is the most significant predictor of Tg, and the two properties can be related through the Boyer-Beaman rule. Herein, we apply a recently developed method utilizing a nano-thermal analysis (nanoTA) module coupled to an atomic force microscope (AFM), to determine the Tm of individual secondary organic aerosol (SOA) particles generated from the reactive uptake of isoprene-derived epoxydiols (IEPOX) onto acidic ammonium sulfate aerosol particles. NanoTA works by using a specialized AFM probe which can be heated while in contact with a particle of interest. As the temperature increases, the probe deflection will first increase due to thermal expansion of the particle followed by a decrease at its Tm. The direct measurements are compared with model predictions based on molecular composition from hydrophilic interaction liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOF-MS) analysis. We compared the Tm of the SOA particles formed from IEPOX uptake onto acidic ammonium sulfate particles created at 30, 65, and 80% relative humidity (RH), and found that increasing RH from 30 to 80% led to an overall decrease in average Tm, indicating less viscous particles at higher RH conditions. Our measurements with this technique will allow for more accurate representations of the phase state of aerosols in the atmosphere. 

The ability of an atmospheric aerosol to take up water or to participate in heterogeneous reactions is highly influenced by its phase state – solid, semi-solid, or liquid. These changes in phase state can be predicted by glass transition temperature (Tg), as particles at temperatures below their Tg will show solid properties, while increasing the temperature above their Tg will allow for semi-solid and eventually liquid properties. Historically, measurements of the Tg of bulk materials have been studied in order to model the phase states of aerosols in the atmosphere; however, these methods only permit an estimation of aerosol Tg based on their bulk chemical composition. Determining the Tg of individual particles will allow for more accurate model predictions of aerosol phase state. Herein, we apply a recently developed method utilizing a nano-thermal analysis (nanoTA) module coupled to an atomic force microscope (AFM), to determine the Tg of individual secondary organic aerosol (SOA) particles generated from the reactive uptake of isoprene epoxydiol (IEPOX) onto acidic ammonium sulfate aerosol particles. NanoTA works by using a specialized AFM probe which can be heated while in contact with a particle of interest. As the temperature increases, the probe deflection will first increase due to thermal expansion of the particle followed by a decrease at its melting temperature (Tm). The Tg of the particle can then be determined from Tm using the Boyer–Beaman rule. We compared the Tg of IEPOX-derived SOA particles generated at relative humidity (RH) of 30, 65, and 80%, and found that increasing RH from 30 to 80% led to a decrease in average Tg of 22 K, indicating less viscous particles at higher RH conditions. Our measurements with this technique will allow for more accurate representations of the phase state of aerosols in the atmosphere. 

Abstract Number: 453 Working Group: Aerosol Chemistry Abstract Secondary organic aerosol (SOA) is composed of a significant fraction of low-volatility high-molecular-weight oligomer products. These species can affect particle viscosity, morphology, and mixing timescales, yet they are not very well understood. While strides have been made in elucidating oligomer formation mechanisms, their degradation is less studied. Previous work suggests that the presence of oligomers may suppress particle mass loss during atmospheric aging by slowing the production high-volatility fragments from monomers. Our work investigates the effects of relative humidity (RH) on oligomer formation in SOA and the effects of hydroxyl radical (·OH) exposure on oligomer degradation. To probe these questions, SOA is generated by the reactive uptake of isoprene epoxydiols (IEPOX) onto acidic ammonium sulfate aerosol in a 2-m3 steady-state chamber, followed by exposure to ·OH in an oxidation flow reactor. We investigate SOA formation at 30-80% RH, which is above and below the deliquescence point of ammonium sulfate. We examine the evolution of SOA bulk chemical composition as well as single-particle physicochemical properties over the course of aging using mass spectrometry-, spectroscopy-, and microscopy-based techniques. An optimized matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) method is used to identify and track the presence of oligomers in SOA over the course of aging. Our research will provide insight about the formation and degradation of oligomers in the atmosphere, which will allow better modeling of their impact on climate. 

Atmospheric aerosols are key contributors to cloud condensation nuclei (CCN) and ice nucleating particle (INP) formation, which can offset positive radiative forcing. Aerosol particles can undergo many cycles of droplet activation and subsequent drying before their removal from the atmosphere through dry or wet deposition. Cloud-aerosol-precipitation interactions are affected by cloud droplet or ice crystal formation, which is related to the physicochemical properties of aerosol particles. Isoprene-derived secondary organic aerosol (iSOA) is an abundant component aerosol and has been previously found in INPs and cloud water residues, and it includes both soluble and insoluble residues in its particle matrix. Currently, most of our understanding of iSOA is derived from studying the soluble residues, but there has been a measurement gap for characterizing the insoluble residues. These measurements are needed as previous research has suggested that insoluble components could be important with respect to CCN and INP formation. Herein, a unique approach is utilized to collect the insoluble residues of SOA in ~3 µm droplets collected from a Spot Sampler from Aerosol Devices, Inc. iSOA is generated by reactive uptake of IEPOX onto acidic seed particles (ammonium sulfate + sulfuric acid) in a humidified atmospheric chamber under dark conditions. Droplets are impacted directly on a substrate or in a liquid medium to study the roles of insoluble residues from both single-particle and bulk perspectives. A suite of microspectroscopy techniques, including Raman and optical photothermal infrared (O-PTIR) spectroscopy, are used to probe the chemical composition of the residues. Atomic force microscopy – photothermal infrared (AFM-PTIR) spectroscopy and Nanoparticle Tracking Analysis (NTA) are used to measure the size distributions of the residues. These insights may help understand the properties of residues from cloud droplet evaporation and subsequent cloud-aerosol-precipitation interactions in the atmosphere. 

We recently demonstrated that the heterogeneous hydroxyl radical (OH) oxidation is an important aging process for isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) that alters its chemical composition, and thus, aerosol physicochemical properties. Notably, dimeric species in IEPOX-SOA were found to heterogeneously react with OH at a much faster rate than monomers, suggesting that the initial oligomeric content of freshly-generated IEPOX-SOA particles may affect its subsequent atmospheric oxidation. Aerosol acidity could in principle influence this aging process by enhancing the formation of sulfated and non-sulfated oligomers in freshly-generated IEPOX-SOA. Many multifunctional organosulfate (OS) products derived from heterogeneous OH oxidation of sulfur-containing IEPOX-SOA have been observed in cloud water residues and ice nucleating particles and could affect the ability of aged IEPOX-SOA particles to act as cloud condensation nuclei. Hence, this study systematically investigated the effect of aerosol acidity on the kinetics and products resulting from heterogeneous OH oxidation of IEPOX-SOA particles. We reacted gas-phase IEPOX with inorganic sulfate particles of varying pH (0.5 to 2.5) in an indoor smog chamber operated under dark, steady-state conditions to form freshly-generated IEPOX-SOA particles. These particles were aged at a relative humidity of 65% in an oxidation flow reactor (OFR) for 0-21 days of equivalent atmospheric OH exposure. Through molecular-level chemical analyses by hydrophilic interaction liquid chromatography method interfaced to electrospray ionization high-resolution quadrupole time- of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS), we observed that highly acidic aerosol has higher oligomer ratio and exhibit much slower mass decay with OH oxidation (pH=0.5, lifetime = 56 days) as compared to less acidic aerosols (pH=2.5, lifetime=17 days). Based on atomic force microscopy (AFM) analysis, aerosol acidity could also affect the morphology and viscosity of IEPOX-SOA during OH oxidation process. 

Abstract We recently demonstrated that the heterogeneous hydroxyl radical (·OH) oxidation is an important aging process for isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) that alters its chemical composition, and thus, aerosol physicochemical properties. Notably, dimeric species in IEPOX-SOA were found to heterogeneously react with ·OH at a much faster rate than monomers, suggesting that the initial oligomeric content of freshly-generated IEPOX-SOA particles may affect its subsequent atmospheric oxidation. Aerosol acidity could in principle influence this aging process by enhancing the formation of sulfated and non-sulfated oligomers in freshly-generated IEPOX-SOA. Many multifunctional organosulfate (OS) products derived from heterogeneous ·OH oxidation of sulfur-containing IEPOX-SOA have been observed in cloud water residues and ice nucleating particles and could affect the ability of aged IEPOX-SOA particles to act as cloud condensation nuclei. Hence, this study systematically investigated the effect of aerosol acidity on the kinetics and products resulting from heterogeneous ·OH oxidation of IEPOX-SOA particles. Gas-phase IEPOX was reacted with inorganic sulfate particles of varying pH (0.5 to 2.0) in an indoor smog chamber operated under dark, steady-state conditions to form freshly-generated IEPOX-SOA particles. These particles were then aged at a relative humidity of 60% in an oxidation flow reactor (OFR) for 0-15 days of equivalent atmospheric ·OH exposure. Aged IEPOX-SOA particles were sampled by an online aerosol chemical speciation monitor (ACSM) to measure real-time aerosol mass and chemical changes of the SOA particles, and were also collected onto Teflon filters and into PILS vials for molecular-level chemical analyses by hydrophilic liquid interaction chromatography method interfaced to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS), ion chromatography, and total OS mass amounts.