8 Search Results

Gas-particle partitioning is critical for the evolution of secondary organic aerosols (SOA) in the atmosphere. SOA particles evaporate more slowly than expected at nearly size-independent rates, but the underlying mechanism remains controversial. Here, in this study, we apply kinetic multilayer modeling to simulate evaporation of α-pinene SOA, demonstrating that surface crust formation, emerging from accumulation of low-volatility compounds at the particle surface, leads to slow evaporation and reduced size dependence of the evaporation rate. While evaporation induced by decomposition of oligomers would naturally lead to size-independent evaporation rates, we observe and simulate nearly size-independent slow evaporation of polyethylene glycol mixturemore » particles containing polymeric species that do not decompose, confirming the relevance of composition-dependent diffusivity for size-independent, slow evaporation. Slow evaporation of limonene SOA was also observed in environmental chamber experiments, and model simulations demonstrate strong surface crust formation with bulk diffusivity being depressed by up to 5 orders of magnitude compared to the inner bulk. We present experimental evidence using a surface-based mass spectrometry technique that shows that the particle surface becomes enriched in high molecular weight compounds upon evaporation of monomers. Our findings imply that viscous surface crusts may also limit the growth and chemical transformation of SOA particles, influencing their impacts on air quality and climate.« less

Isoprene is an abundant volatile organic compound emitted from broadleaf forests. Under low nitric oxide concentrations, isoprene is photochemically oxidized to form gas-phase isoprene epoxydiols (IEPOX). In the presence of acidified sulfate aerosols, IEPOX enhances the secondary organic aerosol (SOA) formation. Predictions of IEPOX-SOA in regional-scale models, e.g., the Community Multiscale Air Quality Model (CMAQ), are uncertain due to homogeneous aerosol assumptions, underpredictions of water uptake (hygroscopicity), and aerosol surface area. Here, we used experimental measurements of IEPOX-SOA tracers, 2-methyltetrols (2-MT) and 2-methyltetrol sulfates (2-MTS), formed at initial IEPOX-to-inorganic sulfate ratios ranging from 1–10.5, at ∼50% relative humidity to constrainmore » key IEPOX-SOA parameters: phase separation, organic shell diffusivity (D_org), acidity, hygroscopic growth, mass accommodation, and kinetics. The base CMAQ parametrization overpredicted experimental IEPOX-SOA with an average normalized mean bias (NMB_average) of 1.63. CMAQ with phase separation underpredicted IEPOX-SOA (NMB_average = −0.71). Using the phase-separated model, CMAQ model performance was optimized (NMB_average = 0.077) with an increased D_org = 2 × 10^–16 m²s^–1 and increased rate constants (k_2-MT = 1 × 10^–3 M² s^–1, k_2-MTS = 8.83 × 10^–3 M² s^–1). The optimized model explicitly accounted for hygroscopic growth by utilizing experimentally derived growth rates, improving aerosol surface area predictions. Our model highlights the importance of the aerosol mixing state (homogeneous versus phase-separated), aerosol size dynamics, and hygroscopic growth in modeling heterogeneous reactive uptake of IEPOX.« less

Aerosol liquid water content (LWC) has been shown to enhance partitioning of water-soluble oxygenated organic vapors into the aerosol particles and facilitate aqueous chemistry, impact SOA formation, composition, and physicochemical properties. Here, this study examines the effect of aerosol liquid water content (LWC) on isoprene SOA formation using effloresced and deliquesced ammonium sulfate ((NH₄)₂SO₄) and sodium chloride (NaCl) seed particles in an environmental chamber with photo-oxidation extending over hours under moderate relative humidity (50%-60%). Our findings indicate that isoprene SOA mass yield is not significantly influenced (p value >> 0.05) by the phase state or the chemical identity of themore » seed particles within a 3–4-hour reaction time scale. Detailed molecular analysis using advanced high resolution mass spectrometry indicates that while both effloresced and deliquesced seed types produced similar molecular formula distributions, deliquesced (NH₄)₂SO₄ slightly favored the production of less volatile compounds. Depth-profiling analysis by single particle mass spectrometry confirmed that isoprene SOA predominantly located on the surfaces of particles with core-shell morphologies, with partial dissolution of the effloresced inorganic salt observed even below the deliquescence relative humidity (DRH) of salt. This finding suggests that assuming dry salt core particles do not interact with SOA coatings, based on salt deliquescence points, may overlook important aqueous chemistry. These results emphasize the critical role of reaction time scale and mixing state on SOA formation and call for further research to understand LWC effects on SOA from different precursors.« less

Nanoplastic particles (NPPs) are emerging anthropogenic pollutants and have been detected in urban, rural, and remote areas. Characterizing the lifetime, fate, and cloud-forming potential of atmospheric NPPs improves our understanding of their environmental processes and climate impacts. This study provides the first quantified heterogeneous reaction rate and lifetime of polystyrene (PS) NPPs against common atmospheric oxidants. The atomized PS NPPs were introduced to a Potential Aerosol Mass (PAM) oxidation flow reactor with ·OH exposure of 0 to 1.5 × 10¹² molecules cm^–3 s, equivalent to atmospheric exposure from 0 to 18 days, assuming an ambient ·OH concentration of 1 ×more » 10⁶ cm^–3. The decay of the PS mass concentration was quantified by monitoring tracer ions, C₆H₆⁺ (m/z 78) and C₈H₈⁺ (m/z 104), by using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The pseudo-first-order rate constant of PS particles reacting with ·OH, k_OH, was determined to be (3.2 ± 0.7) × 10^–13 cm³ molecule^–1 s^–1, equivalent to a half-lifetime of a few hours to ∼80 days in the atmosphere, depending on particle sizes and hydroxyl radical concentrations. The hygroscopicity of 100 nm PS NPPs at different ·OH exposure levels was quantified using a cloud condensation nuclei counter (CCNC), showing a twofold increase of hygroscopicity parameter upon 27 days of atmospheric photooxidation.« less

Chemical transformation of 2-methyltetrol sulfates (2-MTS), key isoprene-derived secondary organic aerosol (SOA) constituents, through heterogeneous hydroxyl radical (^•OH) oxidation can result in the formation of previously unidentified atmospheric organosulfates (OSs). However, detected OSs cannot fully account for the sulfur content released from reacted 2-MTS, indicating the existence of sulfur in forms other than OSs, such as inorganic sulfates. This work investigated the formation of inorganic sulfates through heterogeneous ^•OH oxidation of 2-MTS aerosols. Remarkably, high yields of inorganic sulfates, defined as the moles of inorganic sulfates produced per mole of reacted 2-MTS, were observed in the range from 0.48 ±more » 0.07 to 0.68 ± 0.07. These could be explained by the production of sulfate (SO₄^•-) and sulfite (SO₃^•-) radicals through the cleavage of C-O(S) and (C)O-S bonds, followed by aerosol-phase reactions. Additionally, non-sulfated products resulting from bond cleavage were likely volatile and evaporated into gas phase, as evidenced by observed aerosol mass loss (up to 25%) and concurrent size reduction upon oxidation. This investigation highlights the significant transformation of sulfur from its organic to inorganic forms during the heterogeneous oxidation of 2-MTS aerosols, potentially influencing the physicochemical properties and environmental impacts of isoprene-derived SOA.« less

Secondary organic aerosol (SOA) from acid-driven reactive uptake of isoprene epoxydiols (IEPOX) contributes up to 40% of organic aerosol (OA) mass in fine particulate matter. Our previous work showed substantial conversions of particulate inorganic sulfates to surface-active organosulfates (OSs) by IEPOX decreases aerosol acidity and creates a viscous organic-rich shell that poses as a diffusion barrier, inhibiting additional reactive uptake of IEPOX. In this study, to account for this “self-limiting” effect, a phase-separation box model was developed to evaluate parameterizations of IEPOX reactive uptake against time-resolved chamber measurements of IEPOX-SOA tracers, including 2-methyltetrols (2-MT) and methyltetrol sulfates (MTS), at ~more » 50% relative humidity. The phase-separation model was most sensitive to mass accommodation coefficient, IEPOX diffusivity in the organic shell, and ratio of the third-order reaction rate constants forming 2-MT and MTS (k_MT/k_MTS). In particular, k_MT/k_MTS had to be lower than 0.1 to bring model predictions of 2-MT and MTS in closer agreement with chamber measurements, while prior studies reported values larger than 0.71. The model-derived rate constants favor more particulate MTS formation due to 2-MT likely off-gassing at ambient-relevant OA loadings. Incorporating this parametrization into chemical transport models is expected to predict lower IEPOX-SOA mass and volatility due to the predominance of OSs.« less

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 equilibriummore » 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.« less

Atmospheric aerosols are a significant public health hazard and have substantial impacts on the climate. Secondary organic aerosols (SOAs) have been shown to phase separate into a highly viscous organic outer layer surrounding an aqueous core. This phase separation can decrease the partitioning of semi-volatile and low-volatile species to the organic phase and alter the extent of acid-catalyzed reactions in the aqueous core. A new algorithm that can determine SOA phase separation based on their glass transition temperature (T_g), oxygen to carbon (O:C) ratio and organic mass to sulfate ratio, and meteorological conditions was implemented into the Community Multiscale Airmore » Quality Modeling (CMAQ) system version 5.2.1 and was used to simulate the conditions in the continental United States for the summer of 2013. SOA formed at the ground/surface level was predicted to be phase separated with core–shell morphology, i.e., aqueous inorganic core surrounded by organic coating 65.4 % of the time during the 2013 Southern Oxidant and Aerosol Study (SOAS) on average in the isoprene-rich southeastern United States. Our estimate is in proximity to the previously reported ~70 % in literature. The phase states of organic coatings switched between semi-solid and liquid states, depending on the environmental conditions. The semi-solid shell occurring with lower aerosol liquid water content (western United States and at higher altitudes) has a viscosity that was predicted to be 10²–10¹² Pa s, which resulted in organic mass being decreased due to diffusion limitation. Organic aerosol was primarily liquid where aerosol liquid water was dominant (eastern United States and at the surface), with a viscosity <10² Pa s. Phase separation while in a liquid phase state, i.e., liquid–liquid phase separation (LLPS), also reduces reactive uptake rates relative to homogeneous internally mixed liquid morphology but was lower than aerosols with a thick viscous organic shell. The sensitivity cases performed with different phase-separation parameterization and dissolution rate of isoprene epoxydiol (IEPOX) into the particle phase in CMAQ can have varying impact on fine particulate matter (PM_2.5) organic mass, in terms of bias and error compared to field data collected during the 2013 SOAS. This highlights the need to better constrain the parameters that govern phase state and morphology of SOA, as well as expand mechanistic representation of multiphase chemistry for non-IEPOX SOA formation in models aided by novel experimental insights.« less