Predicting secondary organic aerosol phase state and viscosity and its effect on multiphase chemistry in a regional-scale air quality model

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 acidcatalyzed reactions in the aqueous core. A new algorithm that can determine SOA phase separation based on their glass transition temperature (Tg), oxygen to carbon (O V C) ratio and organic mass to sulfate ratio, and meteorological conditions was implemented into the Community Multiscale Air 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

Α-Pinene-Derived organic coatings on acidic sulfate aerosol impacts secondary organic aerosol formation from isoprene in a box model

Fine particulate matter (PM2.5) is known to have an adverse impact on public health and is an important climate forcer. Secondary organic aerosol (SOA) contributes up to 80% of PM2.5 worldwide and multiphase reactions are an important pathway to form SOA. Aerosol-phase state is thought to influence the reactive uptake of gas-phase precursors to aerosol particles by altering diffusion rates within particles. Current air quality models do not include the impact of diffusion-limiting organic coatings on SOA formation. This work examines how α-pinene-derived organic coatings change the predicted formation of SOA from the acid-catalyzed multiphase reactions of isoprene epoxydiols (IEPOX). A box model, with inputs provided from field measurements taken at the Look Rock (LRK) site in Great Smokey Mountains National Park during the 2013 Southern Oxidant and Aerosol Study (SOAS), was modified to incorporate the latest laboratory-based kinetic data accounting for organic coating influences. Including an organic coating influence reduced the modeled reactive uptake when relative humidity was in the 55–80% range, with predicted IEPOX-derived SOA being reduced by up to 33%. Only sensitivity cases with a large increase in Henry's Law values of an order of magnitude or more or in particle reaction rates resulted in the large statistically significant differences form base model performance. These results suggest an organic coating layer could have an impact on IEPOX-derived SOA formation and warrant consideration in regional and global scale models

Heterogeneous Hydroxyl Radical Oxidation of Isoprene-Epoxydiol-Derived Methyltetrol Sulfates: Plausible Formation Mechanisms of Previously Unexplained Organosulfates in Ambient Fine Aerosols

Methyltetrol sulfates are unique tracers for secondary organic aerosols (SOA) formed from acid-driven multiphase chemistry of isoprene-derived epoxydiols. 2-Methyltetrol sulfate diastereomers (2-MTSs) are the dominant isomers and single most-abundant SOA tracers in atmospheric fine particulate matter (PM2.5), but their atmospheric sinks remain unknown. We investigated the oxidative aging of authentic 2-MTS aerosols by gas-phase hydroxyl radicals (·OH) at a relative humidity of 61 ± 1%. The effective rate constant for this heterogeneous reaction was determined as 4.9 ± 0.6 × 10-13 cm3 molecules-1 s-1, corresponding to an atmospheric lifetime of 16 ± 2 days (assuming an ·OH concentration of 1.5 × 106 molecules cm-3). Chemical changes to 2-MTSs were monitored by hydrophilic interaction liquid chromatography interfaced to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS). Plausible reaction mechanisms are proposed for previously unknown OSs detected in atmospheric PM2.5 at mass-to-charge ratios (m/z) of 139 (C2H3O5S-), 155 (C2H3O6S-), 169 (C3H5O6S-), 171 (C3H7O6S-), 185 (C3H5O7S-), 199 (C4H7O7S-), 211 (C5H7O7S-), 213 (C5H9O7S-), 227 (C5H7O8S-), 229 (C5H9O8S-), and 231 (C5H11O8S-). Heterogeneous ·OH oxidation of 2-MTSs redistributes the particulate sulfur speciation into more oxygenated/functionalized OSs, likely modifying the aerosol physicochemical properties of SOA containing 2-MTSs

Effect of the Aerosol-Phase State on Secondary Organic Aerosol Formation from the Reactive Uptake of Isoprene-Derived Epoxydiols (IEPOX)

Acid-catalyzed reactions between gas- and particle-phase constituents are critical to atmospheric secondary organic aerosol (SOA) formation. The aerosol-phase state is thought to influence the reactive uptake of gas-phase precursors to aerosol particles by altering diffusion rates within particles. However, few experimental studies have explored the precise role of the aerosol-phase state on reactive uptake processes. This laboratory study systematically examines the reactive uptake coefficient (γ) of trans-β-isoprene epoxydiol (trans-β-IEPOX), the predominant IEPOX isomer, on acidic sulfate particles coated with SOA derived from α-pinene ozonolysis. γIEPOX is obtained for core-shell particles, the morphology of which was confirmed by microscopy, as a function of SOA coating thickness and relative humidity. γIEPOX is reduced, in some cases by half of the original value, when SOA coatings are present prior to uptake, especially when coating thicknesses are > 15 nm. The diurnal trend of IEPOX lost to acid-catalyzed reactive uptake yielding SOA compared with other known atmospheric sinks (gas-phase oxidation or deposition) is derived by modeling the experimental coating effect with field data from the southeastern United States. IEPOX-derived SOA is estimated to be reduced by 16-27% due to preexisting organic coatings during the afternoon (12:00 to 7:00 p.m., local time), corresponding to the period with the highest level of production

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed

On the origin of water-soluble organic tracer compounds in fine aerosols in two cities: the case of Los Angeles and Barcelona

Water soluble organic compounds (WSOCs), represented by anhydro-saccharides, dicarboxylic acids and polyols, were analyzed by gas chromatography interfaced to mass spectrometry (GC/MS) in extracts from 103 PM1 and 22 PM2.5 filter samples collected in an urban background and road site in Barcelona (Spain) and an urban background site in Los Angeles (USA), respectively, during one-month intensive sampling campaigns in 2010. Both locations have similar Mediterranean climates, with relatively high solar radiation and frequent anti-cyclonic conditions, and are influenced by a complex mixture of emission sources. Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) analyses were applied on the database in order to resolve differences and similarities in WSOC compositions in the studied sites. Five consistent clusters for the analyzed compounds were obtained, representing primary regional biomass burning organic carbon (regional BBOC), three secondary organic components (aged SOC, isoprene SOC and -pinene SOC), and a less clear component, called urban oxygenated organic carbon (urban OOC). This last component is probably influenced by in-situ urban activities, such as food cooking and traffic emissions and oxidation processes.Peer reviewe

Diurnal cycle of fossil and nonfossil carbon using radiocarbon analyses during CalNex.

Radiocarbon (14C) analysis is a unique tool to distinguish fossil/nonfossil sources of carbonaceous aerosols. We present 14C measurements of organic carbon (OC) and total carbon (TC) on highly time resolved filters (3-4 h, typically 12 h or longer have been reported) from 7 days collected during California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 in Pasadena. Average nonfossil contributions of 58%+/- 15% and 51%+/- 15% were found for OC and TC, respectively. Results indicate that nonfossil carbon is a major constituent of the background aerosol, evidenced by its nearly constant concentration (2-3 gC m-3). Cooking is estimated to contribute at least 25% to nonfossil OC, underlining the importance of urban nonfossil OC sources. In contrast, fossil OC concentrations have prominent and consistent diurnal profiles, with significant afternoon enhancements (similar to 3 gC m-3), following the arrival of the western Los Angeles (LA) basin plume with the sea breeze. A corresponding increase in semivolatile oxygenated OC and organic vehicular emission markers and their photochemical reaction products occurs. This suggests that the increasing OC is mostly from fresh anthropogenic secondary OC (SOC) from mainly fossil precursors formed in the western LA basin plume. We note that in several European cities where the diesel passenger car fraction is higher, SOC is 20% less fossil, despite 2-3 times higher elemental carbon concentrations, suggesting that SOC formation from gasoline emissions most likely dominates over diesel in the LA basin. This would have significant implications for our understanding of the on-road vehicle contribution to ambient aerosols and merits further study