Real-Time Shape-Based Particle Separation and Detailed in Situ Particle Shape Characterization

Particle shape is an important attribute in determining particle properties and behavior, but it is difficult to control and characterize. We present a new portable system that offers, for the first time, the ability to separate particles with different shapes and characterize their chemical and physical properties, including their dynamic shape factors (DSFs) in the transition and free-molecular regimes, with high precision, in situ, and in real-time. The system uses an aerosol particle mass analyzer (APM) to classify particles of one mass-to-charge ratio, transporting them to a differential mobility analyzer (DMA) that is tuned to select particles of one charge, mobility diameter, and for particles with one density, one shape. These uniform particles are then ready for use and/or characterization by any application or analytical tool. We combine the APM and DMA with our single-particle mass spectrometer, SPLAT II, to form the ADS and demonstrate its utility to measure individual particle compositions, vacuum aerodynamic diameters, and particle DSFs in two flow regimes for each selected shape. We applied the ADS to the characterization of aspherical ammonium sulfate and NaCl particles, demonstrating that both have a wide distribution of particle shapes with DSFs from approximately 1 to 1.5

A New Real-Time Method for Determining Particles’ Sphericity and Density: Application to Secondary Organic Aerosol Formed by Ozonolysis of α-Pinene

Particle volumes are most often obtained by measuring particle mobility size distributions and assuming that the particles are spherical. Particle volumes are then converted to mass loads by using particle densities that are commonly estimated from measured mobility and vacuum aerodynamic diameters, assuming that the particles are spherical. For aspherical particles, these assumptions can introduce significant errors. We present in this work a new method that can be applied to any particle system to determine in real time whether the particles are spherical or not. We use our second-generation single particle mass spectrometer (SPLAT II) to measure with extremely high precision the vacuum aerodynamic size distributions of particles that are classified by differential mobility analyzer and demonstrate that the line shape of these vacuum aerodynamic size distributions provide a way to unambiguously distinguish between spherical and aspherical particles. Moreover, the very same experimental system is used to obtain the size, density, composition, and dynamic shape factors of individual particles. We present an application of this method to secondary organic aerosols that are formed as a result of ozonolysis of α-pinene in the presence and absence of an OH scavenger and find these particles to be spherical with densities of 1.198 ± 0.004 and 1.213 ± 0.003 g cm−3, respectively

“Depth-Profiling” and Quantitative Characterization of the Size, Composition, Shape, Density, and Morphology of Fine Particles with SPLAT, a Single-Particle Mass Spectrometer

A significant fraction of atmospheric particles are composed of inorganic substances that are mixed or coated with organic compounds. The properties and behavior of these particles depend on the internal composition and arrangement of the specific constituents in each particle. It is important to know which constituent is on the surface and whether it covers the particle surface partially or entirely. We demonstrate here an instrument consisting of an ultrasensitive single-particle mass spectrometer coupled with a differential mobility analyzer to quantitatively measure in real time individual particle composition, size, density, and shape and to determine which substance is on the surface and whether it entirely covers the particle. For this study, we use NaCl particles completely coated with liquid dioctyl phthalate to generate spherical particles, and NaCl particles partially coated with pyrene, a solid poly aromatic hydrocarbon, to produce aspherical particles with pyrene nodules and an exposed NaCl core. We show that the behavior of the mass spectral intensities as a function of laser fluence yields information that can be used to determine the morphological distribution of individual particle constituents

Evaporation Kinetics of Laboratory-Generated Secondary Organic Aerosols at Elevated Relative Humidity

Secondary organic aerosols (SOA) dominate atmospheric organic aerosols that affect climate, air quality, and health. Recent studies indicate that, contrary to previously held assumptions, at low relative humidity (RH) these particles are semisolid and evaporate orders of magnitude slower than expected. Elevated relative humidity has the potential to affect significantly formation, properties, and atmospheric evolution of SOA particles. Here we present a study of the effect of RH on the room-temperature evaporation kinetics of SOA particles formed by ozonolysis of α-pinene and limonene. Experiments were carried out on α-pinene SOA particles generated, evaporated, and aged at <5%, 50 and 90% RH, and on limonene SOA particles at <5% and 90% RH. We find that in all cases evaporation begins with a relatively fast phase, during which 30–70% of the particle mass evaporates in 2 h, followed by a much slower evaporation rate. Evaporation kinetics at <5% and 50% RH are nearly the same, while at 90% RH a slightly larger fraction evaporates. In all cases, aging the particles prior to inducing evaporation reduces the evaporative losses; with aging at elevated RH leading to a more significant effect. In all cases, the observed SOA evaporation is nearly size-independent

Synergy between Secondary Organic Aerosols and Long-Range Transport of Polycyclic Aromatic Hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs), known for their harmful health effects, undergo long-range transport (LRT) when adsorbed on and/or absorbed in atmospheric particles. The association between atmospheric particles, PAHs, and their LRT has been the subject of many studies yet remains poorly understood. Current models assume PAHs instantaneously attain reversible gas-particle equilibrium. In this paradigm, as gas-phase PAH concentrations are depleted due to oxidation and dilution during LRT, particle-bound PAHs rapidly evaporate to re-establish equilibrium leading to severe underpredictions of LRT potential of particle-bound PAHs. Here we present a new, experimentally based picture in which PAHs trapped inside highly viscous semisolid secondary organic aerosol (SOA) particles, during particle formation, are prevented from evaporation and shielded from oxidation. In contrast, surface-adsorbed PAHs rapidly evaporate leaving no trace. We find synergetic effects between hydrophobic organics and SOA - the presence of hydrophobic organics inside SOA particles drastically slows SOA evaporation to the point that it can almost be ignored, and the highly viscous SOA prevents PAH evaporation ensuring efficient LRT. The data show the assumptions of instantaneous reversible gas-particle equilibrium for PAHs and SOA are fundamentally flawed, providing an explanation for the persistent discrepancy between observed and predicted particle-bound PAHs

Photochemical Aging Alters Secondary Organic Aerosol Partitioning Behavior

Organic aerosol is the largest fraction of the atmospheric nonrefractory aerosol mass and has a significant impact on climate, visibility, and human health. A significant portion of organic aerosol is secondary organic aerosol (SOA), which forms when volatile organic compounds (VOCs) are oxidized and the reaction products partition to the particle phase. SOA formation and aging have been described using semivolatile partitioning theory, and a typical assumption invoked is that gas-particle partitioning rapidly reaches equilibrium. However, several studies have called into question whether traditional equilibrium assumptions are valid, either due to particle-phase diffusion limitations, particle-phase reactions, or liquid/liquid phase separation and immiscibility of organic phases. Here, we investigate the ability of equilibrium partitioning to describe laboratory SOA formation experiments using SOA mass and yield as the evaluation metric. We conduct two types of experiments: (1) co-condensation experiments in which isoprene and α-pinene are simultaneously oxidized to form SOA and (2) sequential condensation experiments in which fresh isoprene SOA is formed in the presence of aged, pre-existing isoprene- or α-pinene-derived SOA particles. In the co-condensation experiments, equilibrium partitioning successfully predicted the time-dependent SOA concentrations, suggesting that the SOA from both precursors rapidly formed a well-mixed phase. However, in the sequential condensation experiments, equilibrium partitioning assumptions significantly overpredicted the observed SOA yield, indicating that freshly formed isoprene SOA did not rapidly partition into either the aged α-pinene or aged isoprene SOA particles to form a well-mixed phase over the 4 h experimental time scale, even at relative humidity as high as 85%. This study shows that an equilibrium partitioning assumption is accurate for freshly formed SOA but that it breaks down after SOA has been photochemically aged for modest amounts of time (15–18 h). These results have important implications for modeling SOA formation and may help to resolve some seemingly divergent conclusions regarding diffusion limitations that exist in the literature

Extreme Molecular Complexity Resulting in a Continuum of Carbonaceous Species in Biomass Burning Tar Balls from Wildfire Smoke

Biomass burning emits a wide range of carbonaceous particles into the atmosphere and has negative impacts on human health and the Earth’s radiative balance. Nonvolatile spherical organic aerosol particles, commonly known as tar balls, represent one of the most abundant particles in aged biomass burning smoke. However, the detailed molecular level composition of ambient tar balls is largely unknown but critical to assess their environmental impacts. Ambient aerosol samples collected during a wildfire event, which were ∼90% tar balls by number fraction, were analyzed using ultrahigh-resolution Orbitrap Elite mass spectrometry with four complementary ionization modes. Our results show the molecular composition of tar balls to be complex, composed of over 10,000 molecular formulas. Model estimated saturation mass concentrations and relative humidity-dependent glass-transition temperatures were consistent with low volatility and solid morphology as expected for tar balls. Room-temperature evaporation kinetics showed that these particles retained ∼90% of their volume after 24 h of evaporation. The molecular complexity detected here signifies a continuum of carbonaceous species, ranging from C3 to C45 with continuous ranges of oxygenation and hydrogen saturation for each Cn. Approximately 24% of molecular formulas were estimated to be highly aromatic, which could indicate chemical compounds with negative health effects and which may contribute to visible light absorption. The carbon continuum observed here has significant implications for the molecular characterization of atmospheric organic matter. The level of complexity detected here should not be ignored in future studies, and we demonstrate that multiple analytical methods may be required to suitably interpret this complexity on a molecular level

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (•OH), singlet molecular oxygen (1O2*), and triplet excited states of organic compounds (3C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase •OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with •OH, 1O2*, and 3C* in cloud droplets and aerosol liquid water. We investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere

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 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. 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