scholarly journals On the implications of aerosol liquid water and phase separation for organic aerosol mass

2017 ◽  
Vol 17 (1) ◽  
pp. 343-369 ◽  
Author(s):  
Havala O. T. Pye ◽  
Benjamin N. Murphy ◽  
Lu Xu ◽  
Nga L. Ng ◽  
Annmarie G. Carlton ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Organic Compounds ◽  
Water Uptake ◽  
Liquid Water ◽  
Transport Model ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Organic Nitrates ◽  
Monitoring Networks ◽  
Chemical Transport Model

Abstract. Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM ∕ OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM ∕ OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH  >  SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM ∕ OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model–measurement gap. When taking into account deviations from ideality, including both inorganic (when RH  >  SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.

scholarly journals On the implications of aerosol liquid water and phase separation for organic aerosol mass

2016 ◽  
Author(s):  
Havala O. T. Pye ◽  
Benjamin N. Murphy ◽  
Lu Xu ◽  
Ng L. Ng ◽  
Annmarie G. Carlton ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Organic Compounds ◽  
Water Uptake ◽  
Liquid Water ◽  
Transport Model ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Organic Nitrates ◽  
Monitoring Networks ◽  
Chemical Transport Model

Abstract. Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM/OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM/OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM/OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically-derived semivolatile species in the CMAQ model were highly water soluble, and expected to contribute to water soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night; but, additional improvements in daytime organic aerosol are needed to close the model-measurement gap. By taking into account deviations from ideality, including both inorganic (when RH > SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.

scholarly journals Functionalization and fragmentation during ambient organic aerosol aging: application of the 2-D volatility basis set to field studies

2012 ◽  
Vol 12 (4) ◽  
pp. 9857-9901 ◽  
Author(s):  
B. N. Murphy ◽  
N. M. Donahue ◽  
C. Fountoukis ◽  
M. Dall'Osto ◽  
C. O'Dowd ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Aqueous Phase ◽  
Transport Model ◽  
Field Studies ◽  
Organic Aerosol ◽  
Basis Set ◽  
Base Case ◽  
Chemical Transport Model ◽  
Heterogeneous Oxidation ◽  
Phase Chemistry

Abstract. Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

scholarly journals A global perspective on aerosol from low-volatility organic compounds

2010 ◽  
Vol 10 (9) ◽  
pp. 4377-4401 ◽  
Author(s):  
H. O. T. Pye ◽  
J. H. Seinfeld
Keyword(s):  
Organic Compounds ◽  
Wet Deposition ◽  
Transport Model ◽  
Organic Aerosol ◽  
Global Perspective ◽  
Chemical Transport Model ◽  
Global Estimate ◽  
Additional Information ◽  
Primary Emissions ◽  
Aerosol Source

Abstract. Global production of organic aerosol from primary emissions of semivolatile (SVOCs) and intermediate (IVOCs) volatility organic compounds is estimated using the global chemical transport model, GEOS-Chem. SVOC oxidation is predicted to be a larger global source of net aerosol production than oxidation of traditional parent hydrocarbons (terpenes, isoprene, and aromatics). Using a prescribed rate constant and reduction in volatility for atmospheric oxidation, the yield of aerosol from SVOCs is predicted to be about 75% on a global, annually-averaged basis. For IVOCs, the use of a naphthalene-like surrogate with different high-NOx and low-NOx parameterizations produces a global aerosol yield of about 30%, or roughly 5 Tg/yr of aerosol. Estimates of the total global organic aerosol source presented here range between 60 and 100 Tg/yr. This range reflects uncertainty in the parameters for SVOC volatility, SVOC oxidation, SVOC emissions, and IVOC emissions, as well as wet deposition. The highest estimates result if SVOC emissions are significantly underestimated (by more than a factor of 2) or if wet deposition of the gas-phase semivolatile species is less effective than previous estimates. A significant increase in SVOC emissions, a reduction of the volatility of the SVOC emissions, or an increase in the enthalpy of vaporization of the organic aerosol all lead to an appreciable reduction of prediction/measurement discrepancy. In addition, if current primary organic aerosol (POA) inventories capture only about one-half of the SVOC emission and the Henrys Law coefficient for oxidized semivolatiles is on the order of 103 M/atm, a global estimate of OA production is not inconsistent with the top-down estimate of 140 Tg/yr by (Goldstein and Galbally, 2007). Additional information is needed to constrain the emissions and treatment of SVOCs and IVOCs, which have traditionally not been included in models.

scholarly journals Gas/particle partitioning of water-soluble organic aerosol in Atlanta

2009 ◽  
Vol 9 (1) ◽  
pp. 635-671 ◽  
Author(s):  
C. J. Hennigan ◽  
M. H. Bergin ◽  
A. G. Russell ◽  
A. Nenes ◽  
R. J. Weber
Keyword(s):  
Organic Carbon ◽  
Liquid Water ◽  
Fine Particle ◽  
Mass Concentration ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Formation Mechanisms ◽  
Main Process ◽  
Aerosol Mass Concentration

Abstract. Gas and particle-phase organic carbon compounds soluble in water (e.g., WSOC) were measured simultaneously in Atlanta throughout the summer of 2007 to investigate gas/particle partitioning of ambient secondary organic aerosol (SOA). Previous studies have established that, in the absence of biomass burning, particulate WSOC (WSOCp) is mainly from secondary organic aerosol (SOA) production. Comparisons between WSOCp, organic carbon (OC) and elemental carbon (EC) indicate that WSOCp was a nearly comprehensive measure of SOA in the Atlanta summertime. To study SOA formation mechanisms, WSOC gas-particle partitioning was investigated as a function of temperature, RH, NOx, O3, and organic aerosol mass concentration. Identifying a clear temperature effect on partitioning was confounded by other temperature-dependent processes, which likely included the emissions of biogenic SOA precursors and photochemical SOA formation. Relative humidity data indicated a linear dependence between partitioning and fine particle liquid water. Lower NOx concentrations were associated with greater partitioning to particles, but WSOC partitioning had no visible relation to O3 or fine particle OC mass concentration. There was, however, a relationship between WSOC partitioning and the WSOCp concentration, suggesting a compositional dependence between partitioning semi-volatile gases and the phase state of the aerosol. Combined, the overall results suggest that partitioning to liquid water, followed by heterogeneous reactions may represent the main process by which SOA is formed in urban Atlanta during summer.

scholarly journals Evidence for ambient dark aqueous SOA formation in the Po Valley, Italy

2016 ◽  
Vol 16 (13) ◽  
pp. 8095-8108 ◽  
Author(s):  
Amy P. Sullivan ◽  
Natasha Hodas ◽  
Barbara J. Turpin ◽  
Kate Skog ◽  
Frank N. Keutsch ◽  
...  
Keyword(s):  
Gas Phase ◽  
Water Uptake ◽  
Liquid Water ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Water Evaporation ◽  
Back Trajectory ◽  
Direct Role ◽  
Po Valley ◽  
Back Trajectory Analysis

Abstract. Laboratory experiments suggest that water-soluble products from the gas-phase oxidation of volatile organic compounds can partition into atmospheric waters where they are further oxidized to form low volatility products, providing an alternative route for oxidation in addition to further oxidation in the gas phase. These products can remain in the particle phase after water evaporation, forming what is termed as aqueous secondary organic aerosol (aqSOA). However, few studies have attempted to observe ambient aqSOA. Therefore, a suite of measurements, including near-real-time WSOC (water-soluble organic carbon), inorganic anions/cations, organic acids, and gas-phase glyoxal, were made during the PEGASOS (Pan-European Gas-AeroSOls-climate interaction Study) 2012 campaign in the Po Valley, Italy, to search for evidence of aqSOA. Our analysis focused on four periods: Period A on 19–21 June, Period B on 30 June and 1–2 July, Period C on 3–5 July, and Period D on 6–7 July to represent the first (Period A) and second (Periods B, C, and D) halves of the study. These periods were picked to cover varying levels of WSOC and aerosol liquid water. In addition, back trajectory analysis suggested all sites sampled similar air masses on a given day. The data collected during both periods were divided into times of increasing relative humidity (RH) and decreasing RH, with the aim of diminishing the influence of dilution and mixing on SOA concentrations and other measured variables. Evidence for local aqSOA formation was only observed during Period A. When this occurred, there was a correlation of WSOC with organic aerosol (R2 = 0.84), aerosol liquid water (R2 = 0.65), RH (R2 = 0.39), and aerosol nitrate (R2 = 0.66). Additionally, this was only observed during times of increasing RH, which coincided with dark conditions. Comparisons of WSOC with oxygenated organic aerosol (OOA) factors, determined from application of positive matrix factorization analysis on the aerosol mass spectrometer observations of the submicron non-refractory organic particle composition, suggested that the WSOC differed in the two halves of the study (Period A WSOC vs. OOA-2 R2 = 0.83 and OOA-4 R2 = 0.04, whereas Period C WSOC vs. OOA-2 R2 = 0.03 and OOA-4 R2 = 0.64). OOA-2 had a high O ∕ C (oxygen ∕ carbon) ratio of 0.77, providing evidence that aqueous processing was occurring during Period A. Key factors of local aqSOA production during Period A appear to include air mass stagnation, which allows aqSOA precursors to accumulate in the region; the formation of substantial local particulate nitrate during the overnight hours, which enhances water uptake by the aerosol; and the presence of significant amounts of ammonia, which may contribute to ammonium nitrate formation and subsequent water uptake and/or play a more direct role in the aqSOA chemistry.

scholarly journals Functionalization and fragmentation during ambient organic aerosol aging: application of the 2-D volatility basis set to field studies

2012 ◽  
Vol 12 (22) ◽  
pp. 10797-10816 ◽  
Author(s):  
B. N. Murphy ◽  
N. M. Donahue ◽  
C. Fountoukis ◽  
M. Dall'Osto ◽  
C. O'Dowd ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Aqueous Phase ◽  
Transport Model ◽  
Field Studies ◽  
Organic Aerosol ◽  
Basis Set ◽  
Base Case ◽  
Chemical Transport Model ◽  
Heterogeneous Oxidation ◽  
Phase Chemistry

Abstract. Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

scholarly journals Rapid deposition of oxidized biogenic compounds to a temperate forest

2015 ◽  
Vol 112 (5) ◽  
pp. E392-E401 ◽  
Author(s):  
Tran B. Nguyen ◽  
John D. Crounse ◽  
Alex P. Teng ◽  
Jason M. St. Clair ◽  
Fabien Paulot ◽  
...  
Keyword(s):  
Dry Deposition ◽  
Transport Model ◽  
Large Fraction ◽  
Surface Concentration ◽  
Water Soluble ◽  
Organic Nitrates ◽  
Chemical Transport Model ◽  
Molecular Diffusivity ◽  
Deposition Velocities ◽  
Simulated Surface

We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m−2⋅s−1). GEOS−Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS−Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.

scholarly journals Gas/particle partitioning of water-soluble organic aerosol in Atlanta

2009 ◽  
Vol 9 (11) ◽  
pp. 3613-3628 ◽  
Author(s):  
C. J. Hennigan ◽  
M. H. Bergin ◽  
A. G. Russell ◽  
A. Nenes ◽  
R. J. Weber
Keyword(s):  
Organic Carbon ◽  
Liquid Water ◽  
Fine Particle ◽  
Mass Concentration ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Formation Mechanisms ◽  
Positive Temperature ◽  
Aerosol Mass Concentration

Abstract. Gas and particle-phase organic carbon compounds soluble in water (e.g., WSOC) were measured simultaneously in Atlanta throughout the summer of 2007 to investigate gas/particle partitioning of ambient secondary organic aerosol (SOA). Previous studies have established that, in the absence of biomass burning, particulate WSOC (WSOCp) is mainly from secondary organic aerosol (SOA) production. Comparisons between WSOCp, organic carbon (OC) and elemental carbon (EC) indicate that WSOCp was a nearly comprehensive measure of SOA in the Atlanta summertime. WSOCp and gas-phase WSOC (WSOCg) concentrations both exhibited afternoon maxima, indicating that photochemistry was a major route for SOA formation. An additional nighttime maximum in the WSOCg concentration indicated a dark source for oxidized organic gases, but this was not accompanied by detectable increases in WSOCp. To study SOA formation mechanisms, WSOC gas/particle partitioning was investigated as a function of temperature, RH, NOx, O3, and organic aerosol mass concentration. No clear relationship was observed between temperature and partitioning, possibly due to a simultaneous effect from other temperature-dependent processes. For example, positive temperature effects on emissions of biogenic SOA precursors and photochemical SOA formation may have accounted for the observed similar proportional increases of WSOCp and WSOCg with temperature. Relative humidity data indicated a linear dependence between partitioning and predicted fine particle liquid water. Lower NOx concentrations were associated with greater partitioning to particles, but WSOC partitioning had no visible relation to O3 or fine particle OC mass concentration. There was, however, a relationship between WSOC partitioning and the WSOCp concentration, suggesting a compositional dependence between partitioning semi-volatile gases and the absorbing organic aerosol. Combined, the overall results suggest two dominant SOA formation processes in urban Atlanta during summer. One was the photochemical production of SOA from presumably biogenic precursors that increased with the onset of sunrise and peaked in the afternoon. The other, which showed no apparent diurnal pattern, involved the partitioning of semi-volatile gases to liquid water, followed by heterogeneous reactions. The co-emission of water vapor and biogenic VOCs from vegetation may link these processes.

scholarly journals Modeling Biomass Burning Organic Aerosol Atmospheric Evolution and Chemical Aging

Atmosphere ◽  
2021 ◽  
Vol 12 (12) ◽  
pp. 1638
Author(s):  
David Patoulias ◽  
Evangelos Kallitsis ◽  
Laura Posner ◽  
Spyros N. Pandis
Keyword(s):  
Dilution Rate ◽  
Organic Compounds ◽  
Biomass Burning ◽  
Transport Model ◽  
Organic Aerosol ◽  
Base Case ◽  
Chemical Transport Model ◽  
Fire Plume ◽  
Case Scenario ◽  
Base Case Scenario

The changes in the concentration and composition of biomass-burning organic aerosol (OA) downwind of a major wildfire are simulated using the one-dimensional Lagrangian chemical transport model PMCAMx-Trj. A base case scenario is developed based on realistic fire-plume conditions and a series of sensitivity tests are performed to quantify the effects of different conditions and processes. Temperature, oxidant concentration and dilution rate all affect the evolution of biomass burning OA after its emission. The most important process though is the multi-stage oxidation of both the originally emitted organic vapors (volatile and intermediate volatility organic compounds) and those resulting from the evaporation of the OA as it is getting diluted. The emission rates of the intermediate volatility organic compounds (IVOCs) and their chemical fate have a large impact on the formed secondary OA within the plume. The assumption that these IVOCs undergo only functionalization leads to an overestimation of the produced SOA suggesting that fragmentation is also occurring. Assuming a fragmentation probability of 0.2 resulted in predictions that are more consistent with available observations. Dilution leads to OA evaporation and therefore reduction of the OA levels downwind of the fire. However, the evaporated material can return to the particulate phase later on after it gets oxidized and recondenses. The sensitivity of the OA levels and total mass balance on the dilution rate depends on the modeling assumptions. The high variability of OA mass enhancement observed in past field studies downwind of fires may be partially due to the variability of the dilution rates of the plumes.

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