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

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.

[1]  Hongyu Guo,et al.  Chemical Characterization of Water-Soluble Organic Aerosol in Contrasting Rural and Urban Environments in the Southeastern United States. , 2017, Environmental science & technology.

[2]  F. Keutsch,et al.  Testing Atmospheric Oxidation in an Alabama Forest , 2016 .

[3]  J. D. de Gouw,et al.  Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) , 2016 .

[4]  J. Thornton,et al.  Fine particle pH and the partitioning of nitric acid during winter in the northeastern United States , 2016 .

[5]  A. Virtanen,et al.  Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US , 2016 .

[6]  C. Hogrefe,et al.  Overview and evaluation of the Community Multiscale Air Quality (CMAQ) model version 5.1 , 2016 .

[7]  S. Martin,et al.  Ambient Gas-Particle Partitioning of Tracers for Biogenic Oxidation. , 2016, Environmental science & technology.

[8]  J. Thornton,et al.  Chemical Characterization of Secondary Organic Aerosol from Oxidation of Isoprene Hydroxyhydroperoxides. , 2016, Environmental science & technology.

[9]  Qi Zhang,et al.  Liquid water: Ubiquitous contributor to aerosol mass , 2016 .

[10]  D. Jacob,et al.  Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US. , 2016, Atmospheric chemistry and physics.

[11]  Naresh Kumar,et al.  Evaluation of the IMPROVE Equation for estimating aerosol light extinction , 2016, Journal of the Air & Waste Management Association.

[12]  A. Chan,et al.  Enhancement in Secondary Organic Aerosol Formation in the Presence of Preexisting Organic Particle. , 2016, Environmental science & technology.

[13]  C. Hennigan,et al.  Drying-Induced Evaporation of Secondary Organic Aerosol during Summer. , 2016, Environmental science & technology.

[14]  W. Asher,et al.  Water Uptake by Organic Aerosol and its Influence on Gas/Particle Partitioning of Secondary Organic Aerosol in the United States , 2016 .

[15]  Nicholas J. Higham,et al.  UManSysProp v1.0: an online and open-source facility for molecular property prediction and atmospheric aerosol calculations , 2016 .

[16]  M. Hallquist,et al.  Molecular Composition and Volatility of Organic Aerosol in the Southeastern U.S.: Implications for IEPOX Derived SOA. , 2016, Environmental science & technology.

[17]  D. Jacob,et al.  Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the Southeast United States and co-benefit of SO2 emission controls. , 2015, Atmospheric chemistry and physics.

[18]  W. Asher,et al.  Molecular view modeling of atmospheric organic particulate matter: Incorporating molecular structure and co-condensation of water , 2015 .

[19]  P. Shepson,et al.  Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States. , 2015, Environmental science & technology.

[20]  P. Shepson,et al.  Understanding isoprene photooxidation using observations and modeling over a subtropical forest in the southeastern US , 2015 .

[21]  A. Lee,et al.  Impacts of Sulfate Seed Acidity and Water Content on Isoprene Secondary Organic Aerosol Formation. , 2015, Environmental science & technology.

[22]  A. Goldstein,et al.  Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements , 2015 .

[23]  J. Thornton,et al.  Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols , 2015 .

[24]  J. Seinfeld,et al.  Isoprene NO_3 Oxidation Products from the RO_2+ HO_2 Pathway , 2015 .

[25]  J. Seinfeld,et al.  Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway. , 2015, The journal of physical chemistry. A.

[26]  D. Jacob,et al.  Sources, seasonality, and trends of southeast US aerosol: an integrated analysis of surface, aircraft, and satellite observations with the GEOS-Chem chemical transport model , 2015 .

[27]  K. Baker,et al.  Evaluation of improved land use and canopy representation in BEIS v3.61 with biogenic VOC measurements in California , 2015 .

[28]  Sri Hapsari Budisulistiorini,et al.  Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia and Look Rock, Tennessee , 2015 .

[29]  Y. Liu,et al.  Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site , 2015 .

[30]  Y. Wang,et al.  Direct atmospheric evidence for the irreversible formation of aqueous secondary organic aerosol , 2015 .

[31]  M. Guzman,et al.  Secondary organic aerosol formation from the β-pinene+NO 3 system: effect of humidity and peroxy radical fate , 2015 .

[32]  Hongyu Guo,et al.  Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates , 2015 .

[33]  A. Carlton,et al.  Decreasing Aerosol Water Is Consistent with OC Trends in the Southeast U.S. , 2015, Environmental science & technology.

[34]  Q. Ying,et al.  Significant Contributions of Isoprene to Summertime Secondary Organic Aerosol in Eastern United States. , 2015, Environmental science & technology.

[35]  S. Martin,et al.  Elemental composition of organic aerosol: The gap between ambient and laboratory measurements , 2015 .

[36]  A. Goldstein,et al.  Gas and aerosol carbon in California: comparison of measurements and model predictions in Pasadena and Bakersfield , 2015 .

[37]  A. Bertram,et al.  Relative humidity-dependent viscosities of isoprene-derived secondary organic material and atmospheric implications for isoprene-dominant forests , 2015 .

[38]  I. Riipinen,et al.  Adsorptive uptake of water by semisolid secondary organic aerosols , 2015 .

[39]  J. Jimenez,et al.  Biomass burning dominates brown carbon absorption in the rural southeastern United States , 2015 .

[40]  J. Crounse,et al.  Rapid deposition of oxidized biogenic compounds to a temperate forest , 2015, Proceedings of the National Academy of Sciences.

[41]  R. J. Thomson,et al.  Uptake of epoxydiol isomers accounts for half of the particle-phase material produced from isoprene photooxidation via the HO2 pathway. , 2015, Environmental science & technology.

[42]  J. Seinfeld,et al.  Influence of particle-phase state on the hygroscopic behavior of mixed organic-inorganic aerosols , 2014 .

[43]  J. R. Hite,et al.  Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States , 2014, Proceedings of the National Academy of Sciences.

[44]  A. Goldstein,et al.  Online derivatization for hourly measurements of gas- and particle-phase semi-volatile oxygenated organic compounds by thermal desorption aerosol gas chromatography (SV-TAG) , 2014 .

[45]  Hongyu Guo,et al.  On the link between hygroscopicity, volatility, and oxidation state of ambient and water-soluble aerosols in the southeastern United States , 2014 .

[46]  Paul A. Solomon,et al.  U.S. National PM2.5 Chemical Speciation Monitoring Networks—CSN and IMPROVE: Description of networks , 2014, Journal of the Air & Waste Management Association.

[47]  J. R. Hite,et al.  Fine-particle water and pH in the southeastern United States , 2014 .

[48]  M. Petters,et al.  Trends in particle-phase liquid water during the Southern Oxidant and Aerosol Study , 2014 .

[49]  G. Yarwood,et al.  1.5-Dimensional volatility basis set approach for modeling organic aerosol in CAMx and CMAQ , 2014 .

[50]  A. Bertram,et al.  Effects of molecular weight and temperature on liquid–liquid phase separation in particles containing organic species and inorganic salts , 2014 .

[51]  M. Petters,et al.  Influence of functional groups on organic aerosol cloud condensation nucleus activity. , 2014, Environmental science & technology.

[52]  J. Seinfeld,et al.  Molecular corridors and kinetic regimes in the multiphase chemical evolution of secondary organic aerosol , 2014 .

[53]  Edward Charles Fortner,et al.  Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications , 2014 .

[54]  S. Madronich,et al.  Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols , 2014 .

[55]  A. Dillner,et al.  Determination of organic matter and organic matter to organic carbon ratios by infrared spectroscopy with application to selected sites in the IMPROVE network , 2014 .

[56]  M. Hannigan,et al.  Gas/particle partitioning of 2-methyltetrols and levoglucosan at an urban site in Denver. , 2014, Environmental science & technology.

[57]  D. Topping,et al.  Including phase separation in a unified model to calculate partitioning of vapours to mixed inorganic-organic aerosol particles. , 2013, Faraday discussions.

[58]  A. Lewis,et al.  Water uptake is independent of the inferred composition of secondary aerosols derived from multiple biogenic VOCs , 2013 .

[59]  A. Bertram,et al.  Liquid–liquid phase separation in particles containing organics mixed with ammonium sulfate, ammonium bisulfate, ammonium nitrate or sodium chloride , 2013 .

[60]  J. Seinfeld,et al.  Organic aerosol formation from the reactive uptake of isoprene epoxydiols (IEPOX) onto non-acidified inorganic seeds , 2013 .

[61]  B. Turpin,et al.  Particle partitioning potential of organic compounds is highest in the Eastern US and driven by anthropogenic water , 2013 .

[62]  Andrew A. May,et al.  Gas-particle partitioning of primary organic aerosol emissions: (1) Gasoline vehicle exhaust , 2013 .

[63]  L. Bartolotti,et al.  A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides. , 2013, Physical chemistry chemical physics : PCCP.

[64]  D. Luecken,et al.  Epoxide pathways improve model predictions of isoprene markers and reveal key role of acidity in aerosol formation. , 2013, Environmental science & technology.

[65]  S. Pandis,et al.  Atmospheric aerosol water-soluble organic carbon measurement: a theoretical analysis. , 2013, Environmental science & technology.

[66]  D. Worsnop,et al.  Real-time continuous characterization of secondary organic aerosol derived from isoprene epoxydiols in downtown Atlanta, Georgia, using the Aerodyne Aerosol Chemical Speciation Monitor. , 2013, Environmental science & technology.

[67]  R. Volkamer,et al.  Effective Henry's law partitioning and the salting constant of glyoxal in aerosols containing sulfate. , 2013, Environmental science & technology.

[68]  J. Jimenez,et al.  On the gas-particle partitioning of soluble organic aerosol in two urban atmospheres with contrasting emissions: 2. Gas and particle phase formic acid: FORMIC ACID PARTITIONING IN LA AND ATLANTA , 2012 .

[69]  G. Pouliot,et al.  Modeling the role of alkanes, polycyclic aromatic hydrocarbons, and their oligomers in secondary organic aerosol formation. , 2012, Environmental science & technology.

[70]  J. Seinfeld,et al.  Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation , 2012 .

[71]  P. Bhave,et al.  Simulating the degree of oxidation in atmospheric organic particles. , 2012, Environmental science & technology.

[72]  E. Edgerton,et al.  Isoprene epoxydiols as precursors to secondary organic aerosol formation: acid-catalyzed reactive uptake studies with authentic compounds. , 2012, Environmental science & technology.

[73]  B. Turpin,et al.  Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies , 2011 .

[74]  A. Bertram,et al.  Predicting the relative humidities of liquid-liquid phase separation, efflorescence, and deliquescence of mixed particles of ammonium sulfate, organic material, and water using the organic-to-sulfate mass ratio of the particle and the oxygen-to-carbon elemental ratio of the organic component , 2011 .

[75]  P. Massoli,et al.  Laboratory studies of the chemical composition and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA) , 2011 .

[76]  J. Pleim,et al.  Surface Flux Modeling for Air Quality Applications , 2011 .

[77]  R. Kamens,et al.  Effect of relative humidity on SOA formation from isoprene/NO photooxidation: enhancement of 2-methylglyceric acid and its corresponding oligoesters under dry conditions , 2011 .

[78]  K. Baker,et al.  Photochemical modeling of the Ozark isoprene volcano: MEGAN, BEIS, and their impacts on air quality predictions. , 2011, Environmental science & technology.

[79]  Jenise L. Swall,et al.  Determining the spatial and seasonal variability in OM/OC ratios across the US using multiple regression , 2010 .

[80]  Allen L. Robinson,et al.  A two-dimensional volatility basis set: 1. organic-aerosol mixing thermodynamics , 2010 .

[81]  Golam Sarwar,et al.  Model representation of secondary organic aerosol in CMAQv4.7. , 2010, Environmental science & technology.

[82]  John H. Seinfeld,et al.  Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols , 2010 .

[83]  Bernard Aumont,et al.  Structure-activity relationships to estimate the effective Henry's law constants of organics of atmospheric interest , 2010 .

[84]  I. Barmpadimos,et al.  Relating hygroscopicity and composition of organic aerosol particulate matter , 2010 .

[85]  P. Wennberg,et al.  Kinetics and products of the acid-catalyzed ring-opening of atmospherically relevant butyl epoxy alcohols. , 2010, The journal of physical chemistry. A.

[86]  J. Seinfeld,et al.  Reactive intermediates revealed in secondary organic aerosol formation from isoprene , 2009, Proceedings of the National Academy of Sciences.

[87]  D. R. Worsnop,et al.  Evolution of Organic Aerosols in the Atmosphere , 2009, Science.

[88]  D. Worsnop,et al.  Physicochemical properties and origin of organic groups detected in boreal forest using an aerosol mass spectrometer , 2009 .

[89]  Armistead G. Russell,et al.  Gas/particle partitioning of water-soluble organic aerosol in Atlanta , 2009 .

[90]  John H. Seinfeld,et al.  Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs) , 2009 .

[91]  M. Bergin,et al.  Correlations between water-soluble organic aerosol and water vapor: a synergistic effect from biogenic emissions? , 2008, Environmental science & technology.

[92]  M. Petters,et al.  A single parameter representation of hygroscopic growth and cloud condensation nucleus activity – Part 2: Including solubility , 2008 .

[93]  T. Onasch,et al.  Collection Efficiencies in an Aerodyne Aerosol Mass Spectrometer as a Function of Particle Phase for Laboratory Generated Aerosols , 2008 .

[94]  J. Pankow,et al.  Variation in the sensitivity of predicted levels of atmospheric organic particulate matter (OPM). , 2008, Environmental science & technology.

[95]  Beiping Luo,et al.  A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients , 2008 .

[96]  B. Pun.  Development and initial application of the sesquiversion of MADRID , 2008 .

[97]  Annmarie G. Carlton,et al.  Oligomers formed through in-cloud methylglyoxal reactions: Chemical composition, properties, and mechanisms investigated by ultra-high resolution FT-ICR mass spectrometry , 2008 .

[98]  J. Pankow,et al.  Organic particulate matter formation at varying relative humidity using surrogate secondary and primary organic compounds with activity corrections in the condensed phase obtained using a method based on the Wilson equation , 2008 .

[99]  C. Marcolli,et al.  A thermodynamic model of mixed organic-inorganic aerosols to predict activity coe ffi , 2008 .

[100]  A. Nenes,et al.  ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K + –Ca 2+ –Mg 2+ –NH 4 + –Na + –SO 4 2− –NO 3 − –Cl − –H 2 O aerosols , 2007 .

[101]  W. Asher,et al.  SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds , 2007 .

[102]  John H. Seinfeld,et al.  Secondary organic aerosol formation from m-xylene, toluene, and benzene , 2007 .

[103]  P. Bhave,et al.  Seasonal and regional variations of primary and secondary organic aerosols over the continental United States: semi-empirical estimates and model evaluation. , 2007, Environmental science & technology.

[104]  Yutaka Kondo,et al.  Oxygenated and water‐soluble organic aerosols in Tokyo , 2007 .

[105]  A. Zelenyuk,et al.  Evaporation of water from particles in the aerodynamic lens inlet: an experimental study. , 2006, Analytical chemistry.

[106]  M. Petters,et al.  A single parameter representation of hygroscopic growth and cloud condensation nucleus activity , 2006 .

[107]  Robert McLaren,et al.  Reactive uptake of glyoxal by particulate matter , 2005 .

[108]  Jay R. Turner,et al.  A method for on‐line measurement of water‐soluble organic carbon in ambient aerosol particles: Results from an urban site , 2004 .

[109]  Donald Dabdub,et al.  A Coupled Hydrophobic-Hydrophilic Model for Predicting Secondary Organic Aerosol Formation , 2003 .

[110]  J. Seinfeld,et al.  Global distribution and climate forcing of carbonaceous aerosols , 2002 .

[111]  Christian Seigneur,et al.  Secondary organic aerosol 2. Thermodynamic model for gas/particle partitioning of molecular constituents , 2002 .

[112]  I. J. Ackermann,et al.  Modeling the formation of secondary organic aerosol within a comprehensive air quality model system , 2001 .

[113]  John H. Seinfeld,et al.  Modeling the Formation of Secondary Organic Aerosol (SOA). 2. The Predicted Effects of Relative Humidity on Aerosol Formation in the α-Pinene-, β-Pinene-, Sabinene-, Δ3-Carene-, and Cyclohexene-Ozone Systems , 2001 .

[114]  R. Dennis Cook,et al.  Detection of Influential Observation in Linear Regression , 2000, Technometrics.

[115]  W. Weathers,et al.  Impact of aerosol liquid water on secondary organic aerosol yields of irradiated toluene/propylene/NOx/(NH4)2SO4/air mixtures , 2000 .

[116]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1998 .

[117]  J. Schnoor.  Environmental Modeling: Fate and Transport of Pollutants in Water, Air, and Soil , 1996 .

[118]  J. Seinfeld,et al.  Gas/Particle Partitioning and Secondary Organic Aerosol Yields , 1996 .

[119]  J. Seinfeld,et al.  Organics alter hygroscopic behavior of atmospheric particles , 1995 .

[120]  J. Pankow.  An absorption model of GAS/Particle partitioning of organic compounds in the atmosphere , 1994 .

[121]  J. Penner,et al.  Large contribution of organic aerosols to cloud-condensation-nuclei concentrations , 1993, Nature.

[122]  W. Shiu,et al.  Illustrated handbook of physical-chemical properties and environmental fate for organic chemicals. Volume 5: pesticide chemicals. , 1992 .