Abstract. Heterogeneous chemistry of oxidized carbons in aerosol phase is known to significantly contribute to secondary organic aerosol (SOA) burdens. TheUNIfied Partitioning Aerosol phase Reaction (UNIPAR) model was developed to process the multiphase chemistry of various oxygenated organics into SOAmass predictions in the presence of salted aqueous phase. In this study, the UNIPAR model simulated the SOA formation from gasoline fuel, which is amajor contributor to the observed concentration of SOA in urban areas. The oxygenated products, predicted by the explicit mechanism, were lumpedaccording to their volatility and reactivity and linked to stoichiometric coefficients which were dynamically constructed by predetermined mathematical equations at different NOx levels and degrees of gas aging. To improve the model feasibility in regional scales, the UNIPAR model was coupled with the Carbon Bond 6 (CB6r3) mechanism. CB6r3 estimated the hydrocarbon consumption and the concentration of radicals (i.e., RO2 and HO2) to process atmospheric aging of gas products. The organic species concentrations, estimated bystoichiometric coefficient array and the consumption of hydrocarbons, were applied to form gasoline SOA via multiphase partitioning andaerosol-phase reactions. To improve the gasoline SOA potential in ambient air, model parameters were also corrected for gas–wall partitioning(GWP). The simulated gasoline SOA mass was evaluated againstmore »
Secondary Organic Aerosol Formation via Multiphase Reaction of Hydrocarbons in Urban Atmosphere Using the CAMx Model Integrated with the UNIPAR model
The prediction of Secondary Organic Aerosol (SOA) in regional scales is traditionally performed by using gas-particle partitioning models. In the presence of inorganic salted wet aerosols, aqueous reactions of semivolatile organic compounds can also significantly contribute to SOA formation. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model utilizes the explicit gas mechanism to better predict SOA formation from multiphase reactions of hydrocarbons. In this work, the UNIPAR model was incorporated with the Comprehensive Air Quality Model with Extensions (CAMx) to predict the ambient concentration of organic matter (OM) in urban atmospheres during the Korean-United States Air Quality (2016 KORUS-AQ) campaign. The SOA mass predicted with the CAMx-UNIPAR model changed with varying levels of humidity and emissions and in turn, has the potential to improve the accuracy of OM simulations. The CAMx-UNIPAR model significantly improved the simulation of SOA formation under the wet condition, which often occurred during the KORUS-AQ campaign, through the consideration of aqueous reactions of reactive organic species and gas-aqueous partitioning. The contribution of aromatic SOA to total OM was significant during the low-level transport/haze period (24-31 May 2016) because aromatic oxygenated products are hydrophilic and reactive in aqueous aerosols. The OM mass predicted with the CAMx-UNIPAR model was more »
- Award ID(s):
- 1923651
- Publication Date:
- NSF-PAR ID:
- 10342767
- Journal Name:
- Atmospheric chemistry and physics
- Volume:
- 22
- ISSN:
- 1680-7324
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Secondary Organic Aerosol (SOA) from diesel fuel is known to be significantly sourced from the atmospheric oxidation of aliphatic hydrocarbons. In this study, the formation of linear-alkane SOA was predicted using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model that simulated multiphase reactions of hydrocarbons. In the model, the formation of oxygenated products from the photooxidation of linear alkanes was simulated using a near-explicit gas kinetic mechanism. Autoxidation paths integrated with alkyl peroxy radicals were added to the Master Chemical Mechanismv3.3.1 to improve the formation of low volatility products in the gas phase and better predict SOA mass. The resulting gas products were then classified into volatility-reactivity based lumping groups that are linked to mass-based stoichiometric coefficients. The SOA mass in the UNIPAR model is produced via three major pathways: partitioning of gaseous oxidized products onto both the organic and wet inorganic phases; oligomerization in organic phase; and aqueous reactions (acid-catalyzed oligomerization and organosulfate formation) in the inorganic phase. The model performance was demonstrated for SOA data that were produced through the photooxidation of a homologous series of linear alkanes ranging from C9 to C15 under varying environments (NOx levels, temperature, and inorganic seed conditions) in a large outdoor photochemicalmore »
-
The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O3, while nighttime chemistry is dominated by the reaction with O3 and NO3 radicals. Here, the diurnal pattern of Secondary Organic Aerosol (SOA) originating from biogenic hydrocarbons was intensively evaluated under varying environmental conditions (temperature, humidity, sunlight intensity, NOx levels, and seed conditions) by using the UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises multiphase gas-particle partitioning and in-particle chemistry. The oxidized products of three different hydrocarbons (isoprene, α-pinene, and β-caryophyllene) were predicted by using near explicit gas mechanisms for four different oxidation paths (OH, O3, NO3, and O(3P)) during day and night. The gas mechanisms implemented the Master Chemical Mechanism (MCM v3.3.1), the reactions that formed low volatility products via peroxy radical (RO2) autoxidation, and self- and cross-reactions of nitrate-origin RO2. In the model, oxygenated products were then classified into volatility-reactivity base lumping species, which were dynamically constructed under varying NOx levels and aging scales. To increase feasibility, the UNIPAR model that equipped mathematical equations for stoichiometric coefficients and physicochemical parameters of lumping species was integrated with the SAPRC gas mechanism. The predictability of the UNIPAR model was demonstrated by simulating chamber-generated SOA data undermore »
-
Abstract. Aromatic hydrocarbons make up a large fraction of anthropogenic volatile organic compounds and contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Four toluene and four 1,2,4-trimethylbenzene (1,2,4-TMB) photooxidation experiments were performed in an environmental chamber under relevantpolluted conditions (NOx∼10 ppb). An extensive suite of instrumentation including two proton-transfer-reaction mass spectrometers (PTR-MS) and two chemical ionisation mass spectrometers (NH4+ CIMS and I− CIMS) allowed for quantification of reactive carbon in multiple generations of hydroxyl radical (OH)-initiated oxidation. Oxidation of both species produces ring-retaining products such as cresols, benzaldehydes, and bicyclic intermediate compounds, as well as ring-scission products such as epoxides and dicarbonyls. We show that the oxidation of bicyclic intermediate products leads to the formation of compounds with high oxygen content (an O:C ratio of up to 1.1). These compounds, previously identified as highly oxygenated molecules (HOMs), are produced by more than one pathway with differing numbers of reaction steps with OH, including both auto-oxidation and phenolic pathways. We report the elemental composition of these compounds formed under relevant urban high-NO conditions. We show that ring-retaining products for these two precursors are more diverse and abundant than predicted by current mechanisms. We present the speciated elemental composition of SOA for both precursorsmore »
-
Abstract. This study presents a characterization of the hygroscopic growth behaviour and effects of different inorganic seed particles on the formation of secondary organic aerosols (SOAs) from the dark ozone-initiated oxidation of isoprene at low NOx conditions. We performed simulations of isoprene oxidation using a gas-phase chemical reaction mechanism based onthe Master Chemical Mechanism (MCM) in combination with an equilibriumgas–particle partitioning model to predict the SOA concentration. Theequilibrium model accounts for non-ideal mixing in liquid phases, includingliquid–liquid phase separation (LLPS), and is based on the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model for mixture non-ideality and the EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature,Intramolecular, and Non-additivity effects) model for pure compound vapourpressures. Measurements from the Cosmics Leaving Outdoor Droplets (CLOUD)chamber experiments, conducted at the European Organization for NuclearResearch (CERN) for isoprene ozonolysis cases, were used to aid inparameterizing the SOA yields at different atmospherically relevanttemperatures, relative humidity (RH), and reacted isoprene concentrations. To represent the isoprene-ozonolysis-derived SOA, a selection of organicsurrogate species is introduced in the coupled modelling system. The modelpredicts a single, homogeneously mixed particle phase at all relativehumidity levels for SOA formation in the absence of any inorganic seedparticles. In the presence ofmore »