Introduction
Water is a ubiquitous component of atmospheric aerosol , which can interact with organic compounds in a number of ways to influence particulate matter (PM) mass and size, human health, and Earth's radiative balance. While constituents such as sulfate and nitrate often drive aerosol water concentrations, inorganic and organic compounds are internally mixed under humid conditions , and hydrophilic organic compounds promote the uptake of water . Uptake of water into the organic phase increases particle size, making particles more effective at interacting with radiation , obscuring visibility , and forming clouds . Water can serve as a medium for partitioning of soluble and semivolatile gases, thus contributing to particulate matter concentrations. Once in the particle phase, organic compounds can participate in water-mediated reactions such as hydrolysis, driving isoprene epoxydiol uptake to the particle and loss of gas-phase organic nitrates .
Organic–aerosol-water interactions have been examined in a number of laboratory and field studies, and results are mixed. The lack of a consistent relationship in laboratory work may be partially due to experimental conditions such as high mass loadings that minimize the effect of water for semivolatile systems . Laboratory studies have observed no significant change in yield with increasing relative humidity (RH) , enhanced yields under dry conditions , and higher yields with increasing aerosol water depending on the precursor, oxidant, and seed. Trends in ambient aerosol organic carbon are consistent with the trend in decreasing aerosol water in the southeast US , and observed episodic correlations of water-soluble organic carbon and water vapor. However, found no well-defined relationship over the entire summer in Atlanta, GA, and organic aerosol was not correlated with liquid water content in Pittsburgh, PA . found that the presence of organic compounds suppressed aerosol water in urban locations. In the atmosphere, the relative roles of different secondary organic aerosol (SOA) species change as a function of time and space, and each species may have a different sensitivity to aerosol water.
The interaction of primary organic aerosol (POA), SOA from low-volatility and semivolatile ( ) compounds, SOA from aqueous pathways, and the inorganic/water-rich phase is important for the concentration of organic aerosol (OA) as partitioning is a function of the availability of an absorptive medium. Current chemical transport models, including the Community Multiscale Air Quality (CMAQ) model , consider SOA to be exclusively or dominantly formed via condensation of organic compounds in the absence of water. Individual model studies have examined hydrophobic and hydrophilic SOA through semi-mechanistic algorithms and surrogate structure information. used a decoupled approach in which organic species partitioned only to their dominant phase (aqueous vs. organic). allowed compounds to partition to both phases in varying amounts based on their properties. examined the implications of water uptake to the organic phase and the effects on OA concentrations. allowed organic compounds to interact with water and separate into two phases if thermodynamically favorable. None of these approaches considered mixing of the inorganic and organic phases and often required computationally intensive calculations of activity coefficients. These models accounting for aerosol-water–organic interactions are not in widespread use and have not been evaluated with recently available observations of aerosol water.
Figure shows the contribution of POA and water-soluble OA (determined from water-soluble organic carbon, WSOC; ) to total OA as observed during the Southern Oxidant and Aerosol Study (SOAS) for June 2013 in Centreville, AL. Ambient measurements of WSOC are highly correlated with oxygenated organic aerosol (OOA) , and water-soluble OA accounted for 90 % of total OA on average in the southeast US during summer 2013 . WSOC has also been proposed to contain SOA from aqueous pathways with evidence for reversible and irreversible formation. CMAQ tends to overpredict the concentration of POA by almost a factor of 2 during SOAS . CMAQ predicts a relatively minor role for aqueous OA with the dominant source of OA in CMAQ being dry processes (other SOA in Fig. ).
Contribution of POA
[Figure omitted. See PDF]
Through a series of sensitivity simulations (outlined in Sect. ), this work aims to understand if interactions of aerosol water with semivolatile compounds can resolve model–measurement discrepancies and to what degree OA predicted by models should be classified as water soluble. Semiempirical SOA in the CMAQ model (Sect. ) was connected to a consistent set of properties useful for predicting atmospherically relevant behavior such as interaction with aerosol water. In cases where a specific molecular species was not already used as a surrogate, aerosol properties were linked to volatility and parent hydrocarbon (Sect. ). These quantities allowed molecular weights, organic matter to organic carbon (OM OC) ratios, Henry's law coefficients, deposition properties, hygroscopicity (), phase separation (Sect. ), water uptake (Sect. ), and deviations from ideality (Sect. ) to be predicted semiempirically and influence partitioning (Sect. ). In addition, the fraction WSOC was estimated for model species (Sect. ), and primary vs. secondary organic aerosol was estimated for monitoring networks (Sect. ). The property updates will be available in CMAQ v5.2, and their effects on model predictions are illustrated in Sect. . The implications of the updates for OA and particle-phase liquid water content (LWC) are examined in the context of routine monitoring networks and Southern Oxidant and Aerosol Study (SOAS) observations (Sect. ).
Method
Simulations
CMAQ v5.1 with additional updates was run over the eastern United States for June 2013 at 12 km by 12 km horizontal resolution using the same domain and meteorological inputs as in the work of . Anthropogenic emissions were based on the EPA National Emission Inventory (NEI) 2011 v1. Isoprene emissions were predicted with the Biogenic Emission Inventory System (BEIS) v3.6.1 . BEIS often predicts lower emissions than the Model of Emissions of Gases and Aerosols from Nature (MEGAN) , and isoprene emissions were increased by 50 % in this work to better agree with observations of isoprene and OH at the SOAS Centreville, AL (CTR), site (Fig. S1i–h in the Supplement).
A baseline simulation including surrogate property updates detailed in Sect. (molecular weight, Henry's law coefficients, etc.) and three sensitivity simulations examining the implications of aerosol liquid water for SOA were conducted (Fig. ). In the baseline simulation, POA and traditional SOA were designated hydrophobic and did not interact with aerosol water or SOA produced through aqueous pathways following common chemical transport model assumptions. Two sensitivity simulations examined the implications of aerosol water on semivolatile partitioning via increases in the partitioning medium assuming ideal mixing. In one simulation (ideal ), POA, traditional SOA, aqueous SOA, and water associated with inorganic constituents were assumed to form one ideal phase when RH was above the separation relative humidity (SRH) and to undergo liquid–liquid phase separation into organic-rich (POA and traditional SOA) and water-rich (aqueous SOA and inorganic constituents) ideal phases otherwise. When one phase was predicted to be present (SRH RH), interactions of semivolatile organic compounds and inorganic water were assumed to be ideal. When phase separation occurred, semivolatile organic compounds did not interact with water. In the second simulation, uptake of water to the organic phase () was predicted based on its OM OC and -Köhler theory (Sect. ). Thus, ideal and simulations are meant to capture the effects of inorganic and organic water under ideal conditions separately. The impacts of phase separation and water uptake to organic species along with deviations from ideality determined via an activity coefficient () were simulated together in the third sensitivity simulation ().
Interactions of the inorganic phase (e.g., sulfate, nitrate, ammonium, aerosol water), aqueous SOA, vapor-pressure-driven SOA, and POA in the base and sensitivity simulations. Blue arrows depict water partitioning/uptake. Red arrows indicate semivolatile partitioning interactions via modified Raoult's law. The white dashed arrows indicate aqueous SOA interaction with the inorganic phase (via liquid water, acidity, and particle size).
[Figure omitted. See PDF]
CMAQ organic aerosol
CMAQ v5.1 contains several types of SOA with different sensitivities to aerosol water: traditional semivolatile SOA from Odum two-product representations, nonvolatile SOA produced by volatile organic compound (VOC) reaction, heterogeneously produced SOA parameterized by an uptake coefficient, semivolatile organic nitrate SOA and its hydrolysis product, and other contributions from cloud processing and accretion/oligomerization reactions (Fig. , Table ). The traditional SOA systems in CMAQ include SOA from isoprene, monoterpenes, sesquiterpenes, benzene, toluene, xylene, alkanes, and polycyclic aromatic hydrocarbons (PAHs) . The semivolatile SOA from these precursors is allowed to oligomerize to a nonvolatile form on a 29 h timescale . Currently, low- oxidation of aromatics leads to nonvolatile SOA in the traditional systems. Glyoxal (GLY), methylglyoxal, and epoxides undergo heterogeneous uptake to form SOA . Glyoxal SOA forms using a fixed uptake coefficient of 0.0029 . Following the approach of , methylglyoxal's uptake coefficient was scaled to the glyoxal uptake coefficient by the relative Henry's law coefficient (resulting in an uptake coefficient of ) in this work. Isoprene epoxydiol (IEPOX) SOA is parameterized with an uptake coefficient calculated as a function of aerosol phase constituents, including sulfate and water assuming an acid-catalyzed mechanism . In this work, the IEPOX organosulfate formation rate constant was updated to using the ratio of 2-methyltetrol to organosulfate formation rate constants from and a 2-methyltetrol rate constant of . This organosulfate rate constant is more aggressive (overall and relative) than predicted by . Overestimates of the organosulfate in the model may compensate for missing IEPOX-derived SOA species such as -alkene triols or additional oligomers . In addition, the Henry's law coefficient was updated to , which improved model predictions of 2-methyltetrols (Supplement) and total isoprene SOA. The diffusivity of IEPOX in the particle (, ) was predicted by fitting a line through the data in the work of resulting in for . Semisolid organic aerosol ( ) is not expected in the humid eastern US during summer . SOA from later-generation high-/high- SOA species (methacrylic acid epoxide and hydroxymethyl-methyl--lactone) is relatively minor , consistent with observations from SOAS ground sites . All SOA produced through heterogeneous uptake is assumed to be nonvolatile in CMAQ v5.1. SOA from isoprene and monoterpene organic nitrates is semivolatile, but the nitrate groups hydrolyze in the particle to produce SOA, which is assumed to be nonvolatile, and nitric acid . SOA from cloud processing is predicted to result in less than 3 % of total organic aerosol in CMAQ. POA and volatility-based SOA is treated as hydrophobic by default, while aqueous and in-cloud SOA is assumed to be hydrophilic and resides in a water-rich phase (CMAQv5.1 aero6i assumptions; Table ).
Schematic of SOA treatment in current CMAQ-aero6i. Species are described in Table . Species in grey boxes are nonvolatile. Species with names in red make up POA (i.e., POA POC NCOM, where POC stands for primary organic carbon and NCOM stands for non-carbon organic matter). Species with names in blue form in the model as a direct result of interactions with water.
[Figure omitted. See PDF]
SOA and semivolatile organic compound (SVOC) species in CMAQ v5.1-aero6i . CMAQ model species names are generally preceded by the letter A to indicate aerosol. Semivolatile surrogates have a corresponding gas-phase species whose name is preceded by the letters SV.
Species | Species or production pathway description | Partitioning medium in CMAQ v5.1 |
---|---|---|
ALK1 | alkane OH SOA/SVOC | Dry organic aerosol |
ALK2 | alkane OH SOA/SVOC | Dry organic aerosol |
BNZ1 | benzene OH high- SOA/SVOC | Dry organic aerosol |
BNZ2 | benzene OH high- SOA/SVOC | Dry organic aerosol |
BNZ3 | benzene OH low- SOA | Dry organic aerosol |
DIM | IEPOX-derived dimers | Aqueous aerosol |
GLY | glyoxal methylglyoxal SOA | Aqueous aerosol |
IEOS | IEPOX-derived organosulfate | Aqueous aerosol |
IETET | 2-methyltetrols | Aqueous aerosol |
IMGA | 2-methylglyceric acid | Aqueous aerosol |
IMOS | MPAN-derived organosulfate | Aqueous aerosol |
ISO1 | isoprene OH SOA/SVOC | Dry organic aerosol |
ISO2 | isoprene OH SOA/SVOC | Dry organic aerosol |
ISO3 | acid-catalyzed isoprene SOA | Dry organic aerosol |
ISOPNN | isoprene dinitrate | Dry organic aerosol |
MTHYD | organic nitrate hydrolysis product | Aqueous aerosol (from dry organic aerosol parent) |
MTNO3 | monoterpene nitrate | Dry organic aerosol |
OLGA | oligomers from anthropogenic SOA/SVOCs | Dry organic aerosol |
OLGB | oligomers from biogenic SOA/SVOCs | Dry organic aerosol |
ORGC | glyoxal+methylglyoxal SOA | Cloud droplets |
PAH1 | naphthalene OH high- SOA/SVOC | Dry organic aerosol |
PAH2 | naphthalene OH high- SOA/SVOC | Dry organic aerosol |
PAH3 | naphthalene OH low- SOA | Dry organic aerosol |
SQT | sesquiterpene OH, , , SOA/SVOC | Dry organic aerosol |
TOL1 | toluene OH high- SOA/SVOC | Dry organic aerosol |
TOL2 | toluene OH high- SOA/SVOC | Dry organic aerosol |
TOL3 | toluene OH low- SOA | Dry organic aerosol |
TRP1 | monoterpene OH, , SOA/SVOC | Dry organic aerosol |
TRP2 | monoterpene OH, , SOA/SVOC | Dry organic aerosol |
XYL1 | xylene OH high- SOA/SVOC | Dry organic aerosol |
XYL2 | xylene OH high- SOA/SVOC | Dry organic aerosol |
XYL3 | xylene OH low- SOA | Dry organic aerosol |
AISO3 contains the sum of 2-methyltetrols and IEPOX-derived organosulfates in CMAQv5.1-aero6. It is not used in aero6i as those species are represented individually. Prior to v5.1, AISO3 was determined as an enhancement over AISO1 AISO2 based on [H] .
Updating properties of semivolatiles
Molecular properties
For SOA systems, the molecular weight and OM OC by mass must be
specified for mass-to-molecule number unit conversions within CMAQ and to
allow for post-processing of organic carbon (OC) from total SOA for
comparison to observations. The number of carbons per molecule
() is also specified for the traditional semivolatile systems
to allow for oligomerization to conserve carbon .
Historically, in CMAQ model formulations (v5.1 and prior), the
, saturation concentration (), and OM OC were
set independently with the OM OC obtained from chamber experiments and
set to that of the parent hydrocarbon. The molecular weight
was calculated to be consistent with the number of carbons and OM OC.
The OM OC values were not a function of volatility or peroxy radical
() fate. Thus, all SOA species from a given parent hydrocarbon
were assumed to have the same properties (OM OC, molecular weight,
number of carbons) regardless of their volatility. When viewed in the O : C
vs. space , this leads to some apparent
contradictions such as sesquiterpene SOA being more functionalized and having
a longer carbon backbone at a given vapor pressure than isoprene or
monoterpene SOA. This inconsistency is also seen in the molecular weight vs.
space (Fig. ). Most SOA constituents are
expected to show that molecular weight is correlated with vapor pressure
() with more functionalized species having a shallower slope than
less functionalized species . Systems examined by
were found to reside between a line characteristic of
O : C (alkane, ) and O : C (sugar,
). Sesquiterpene SOA in CMAQ v5.1 resides outside the
molecular corridor bounds that correspond to O : C (OM OC=1.17)
and O : C (OM OC to 2.5). The CMAQv5.1 Odum two-product
isoprene SOA components imply an O : C
The volatility, molecular weight, and OM OC of SOA species in CMAQ. Nonvolatile species are arbitrarily plotted at a saturation concentration of 0.01 . The arrows start at the old molecular weights assumed in CMAQ v5.1. The arrows end at the new (CMAQ v5.2) molecular weights in Table . Lines indicate the properties of alkanes and sugars. The molecular weight of sesquiterpene SOA in CMAQ v5.1 is off the scale at 378 g mol.
[Figure omitted. See PDF]
Structure–activity relationships or group contribution methods can be used to
relate vapor pressure, molecular weight, and OM OC (or molar O : C).
developed a relationship between the saturation
concentration of a pure species ( ), number of
carbons per molecule, and number of oxygens per molecule ()
ignoring sulfate and nitrate for use with the 2-D volatility basis set (VBS):
Built into this relationship are assumptions about the functionality of
semivolatile organic compounds (specifically equal alcohols and ketones with
acid terminal groups), the volatility of a 25 carbon alkane (
), and how a given functional group affects volatility
Deposition properties
The deposition-related properties of gases, such as their solubility, diffusivity, and reactivity, are related to molecular structure and composition. CMAQ uses a resistance in series method for dry deposition . CMAQ v4.7 through v5.1 use adipic acid (Henry's law coefficient, ) as a wet deposition surrogate for gas-phase semivolatile organic compounds (SVOCs). Default dry deposition of SVOCs is based on acetic acid ( ; gas-phase diffusivity ( 0.0944 ; dry cuticular resistance 1200 ; LeBas molar volume 63 ).
used the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO) to predict products from various SOA systems commonly represented in models. Henry's law coefficients were then estimated based on the GROup contribution Method for Henry's law Estimate (GROMHE) . GROMHE was found to reproduce Henry's Law coefficients for organic–water systems with a mean absolute error of about 0.3 log units compared to 0.5 for HenryWin and 0.4 for SPARCv4.2 (SPARC Performs Automated Reasoning in Chemistry; ). For SOA systems, a strong relationship was observed between saturation concentrations and Henry's law coefficients, with chemically aged species being less volatile, more functionalized, and more soluble than their parent hydrocarbon. Although the relationship between and was relatively robust, variability in spanned many orders of magnitude for a given bin without considering how inorganic species may modify the Henry's law coefficient. The relationships derived by were used to predict the Henry's law coefficients as a function of for each SVOC surrogate in equilibrium with the particle in the model. An enthalpy of solvation of 50 was also adopted to adjust the Henry's law coefficients for temperature. Note that although the approach used by is also a group contribution method, it potentially represents the functional groups present in CMAQ SOA species with different groups than would be assumed by Eqs. ()–().
Additional properties needed for deposition include the gas-phase diffusion coefficient, which was calculated as a function of molecular weight via , and the LeBas molar volume (), calculated assuming ring-opened products : where the number of hydrogens, , is calculated from the molecular weight assuming only carbon, oxygen, and hydrogen. Modifications were also made to the deposition parameters affecting , IEPOX, and organic nitrates to produce results consistent with (parameters available in the Supplement).
Predicting phase separation
The solubility of an organic compound in water generally decreases due to the addition of a salt with some exceptions, like glyoxal . However, as atmospheric aerosols contain water, salts, and organic compounds, there are likely conditions where the solubility of an organic is more or less favorable in the water–inorganic-rich phase. Mixed organic–inorganic solutions have been observed to phase-separate into an organic-rich and inorganic-rich phase based on their degree of functionalization (as measured by O : C) and relative humidity. The O : C serves as a proxy for molar polarization, which dictates the magnitude of the salting-out effect through the Setchenov equation . The relative humidity above which a single combined phase exists is called the separation relative humidity. The SRH is not expected to be a strong function of the organic-to-inorganic ratio , molecular weight of the organic species, or temperature between 244 and 290 K . However, the SRH is a function of the type of salt present, with ammonium sulfate having higher SRH (and less frequent mixing) than ammonium bisulfate, sodium chloride, and ammonium nitrate for a given O : C. During SOAS, inorganic aerosol was dominated by and , and SRH was diagnosed in CMAQ based on the experimental results for ammonium sulfate. The relationship for SRH (fraction between 0 and 1) as a function of O : C was recast in terms of OM OC: Since ammonium sulfate has the highest SRH of the salts examined by , choosing another salt would increase the frequency of phase mixing and difference compared to the base simulation.
For simulations considering phase separation in CMAQ (ideal and ), when the ambient relative humidity was below the SRH, the model separated the particle into a water-rich phase (containing aqueous SOA) and an organic-rich phase (containing traditional SOA and POA). This separation of aqueous SOA and traditional SOA at low RH is consistent with the work of , who found that isoprene SOA surrogates unfavorably interacted with -pinene SOA even at 60 % RH.
Predicting water uptake to the organic phase
Water uptake to the organic phase ( and simulations) was predicted in CMAQ using -Köhler theory and solving for the volume-equivalent diameter, : and where is the volume () equivalent accumulation mode diameter excluding water associated with organic species, is the molecular weight of water, is the density of water, is the universal gas constant, is temperature, and is the surface tension of water (0.072 J ). In order to calculate the volume-equivalent diameters, and , particle density was needed. Density values in CMAQ v4.7–v5.1 for organic constituents are generally on the order of 2000 . The densities of organic aerosol species were updated to chamber-specific information when available and to 1400 otherwise. The mass of particle liquid water associated with organic compounds per volume of air () was calculated from where was number of particles per volume air. Total aerosol water in the model was computed as the sum of water associated with inorganics () calculated with ISORROPIA v2.2 and .
The hygroscopicity parameter, , was calculated as a volume-weighted sum of the individual component ignoring water associated with organics:
Cloud condensation nuclei (CCN)-based s were used following due to the completeness of that study. The O : C values obtained by were increased by 27 % to account for a low bias in old calibrations . In addition, the relationship was recast in terms of OM OC, resulting in Equations in terms of O : C are available in the Supplement.
For subsaturated conditions, like those relevant to predicting water uptake, the hygroscopic growth factor (hgf) is most relevant ; however, CMAQ simulations used CCN-based to predict water uptake. Hgf-based s from and were combined with data from into a parameterization by . After correcting the parameterization to use updated O : C, the parameterization including hgf-based data resulted in one negative and three s higher than 0.6 (same as ammonium sulfate), which may be an upper limit on . Thus, contrary to the typical trend of , more than half of the species had . Variation from study to study may be higher than vs. variations, which have been found to be within 30 % for many compounds and unable to be resolved using common measurement techniques .
In the processing of model output, the following equation was used to determine how errors in the concentration of organic compounds ([OA]), , and RH propagated to errors in : with the activity of water () defined as
Representing the effect of water on semivolatile partitioning
Partitioning of semivolatile organic species into an absorbing medium can be described by a modified Raoult's law : where is the aerosol phase concentration of species (), is the gas-phase concentration of (), is the mass of the partitioning medium (), is the molecular weight of the partitioning medium, is a mole-based activity coefficient, and is the saturation vapor pressure of pure . This relationship (Eq. ) is true regardless of how the partitioning coefficient ( or ) is defined. CMAQ, following , defines as where the relevant molecular weight is the individual species molecular weight in contrast to the traditional definition of , which uses the partitioning medium's molecular weight: Model calculations in this work used the definition in Eq. thus: where the total moles in the partitioning medium () are represents aerosol in the partitioning medium that is not semivolatile during calculation. Including water in the partitioning medium (either from uptake onto hydrophilic organic compounds or from the inorganic phase) increases the moles of partitioning medium by contributing to . The inclusion of water, and even inorganic constituents, in the absorbing phase has been encouraged for simplified models in order to reproduce more detailed calculations .
One equation for one unknown can be derived, where is the total () mass of the semivolatile determined by the mass-based stoichiometric coefficients and amount of parent hydrocarbon reacted (HC): Equation was solved for in the model.
for the interpretation of data from chamber experiments only, and it allows for in a single-precursor chamber experiment so that the Odum two-product fit can be determined. Table indicates this was a realistic assumption for most systems as the two surrogate molecular weights vary by less than 10 %. This assumption was not necessary within the CMAQ model.
A priori SOA and SVOC properties: saturation concentration of pure species (), mass-based stoichiometric yield from parent hydrocarbon reaction (), organic matter to organic carbon ratio (OM OC), molecular weight (), number of carbons per molecule (), Henry's law coefficient (), diffusivity in the gas phase (), LeBas molar volume (), hygroscopicity parameter (), density (), activity coefficient at infinite dilution (), solubility (), and saturation concentration at infinite dilution in water (). All temperature-dependent parameters given at 298 K.
Species | OM OC | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
ALK1 | 0.1472 | 0.0334 | 1.56 | 225 | 12 | 0.0514 | 280.5 | 0.07 | 1400 | 5600 | 2 | ||
ALK2 | 51.8775 | 0.2164 | 1.42 | 205.1 | 12 | 0.0546 | 275.6 | 0.06 | 1400 | 2000 | 6 | ||
BNZ1 | 0.302 | 0.0720 | 2.68 | 161 | 5 | 0.0642 | 134.1 | 0.19 | 1400 | 5800 | 2 | ||
BNZ2 | 111.11 | 0.8880 | 2.23 | 134 | 5 | 0.0726 | 127.5 | 0.15 | 1400 | 1400 | 5 | ||
BNZ3 | NA | 0.370 | 3.00 | 180 | 5 | NA | NA | NA | 0.23 | 1400 | NA | NA | |
DIM | NA | NA | 2.07 | 248.2 | 10 | NA | NA | NA | 0.13 | 1400 | NA | NA | NA |
GLY | NA | NA | 2.13 | 66.4 | 3 | NA | NA | NA | 0.13 | 1400 | NA | NA | NA |
IEOS | NA | NA | 3.60 | 216.2 | 5 | NA | NA | NA | 0.30 | 1400 | NA | NA | NA |
IETET | NA | NA | 2.27 | 136.2 | 5 | NA | NA | NA | 0.15 | 1400 | NA | NA | NA |
IMGA | NA | NA | 2.50 | 120.1 | 4 | NA | NA | NA | 0.18 | 1400 | NA | NA | NA |
IMOS | NA | NA | 4.17 | 200.2 | 4 | NA | NA | NA | 0.36 | 1400 | NA | NA | NA |
ISO1 | 116.01 | 0.2320 | 2.20 | 132 | 5 | 0.0733 | 126.3 | 0.14 | 1400 | 60 | 120 | ||
ISO2 | 0.617 | 0.0288 | 2.23 | 133 | 5 | 0.0729 | 123.8 | 0.15 | 1400 | 130 | 56 | ||
ISO3 | NA | NA | 2.80 | 168.2 | 5 | NA | NA | NA | 0.21 | 1400 | NA | NA | NA |
ISOPNN | 8.9 | NA | 3.80 | 226 | 5 | 0.0457 | 206.8 | 0.32 | 1400 | 130 | 98 | ||
MTHYD | NA | NA | 1.54 | 185 | 10 | NA | NA | NA | 0.07 | 1400 | NA | NA | NA |
MTNO3 | 12 | NA | 1.90 | 231 | 10 | e,f | 0.0453 | 251.2 | 0.11 | 1400 | 29 000 | 0.4 | |
OLGA | NA | NA | 2.50 | 206 | 7 | NA | NA | NA | 0.18 | 1400 | NA | NA | |
OLGB | NA | NA | 2.10 | 248 | 10 | NA | NA | NA | 0.13 | 1400 | NA | NA | |
ORGC | NA | NA | 2.00 | 177 | 7 | NA | NA | NA | 0.12 | 1400 | NA | NA | NA |
PAH1 | 1.6598 | 0.2100 | 1.63 | 195.6 | 10 | 0.0564 | 235.7 | 0.08 | 1480 | 5300 | 2 | ||
PAH2 | 264.6675 | 1.0700 | 1.49 | 178.7 | 10 | 0.0599 | 231.5 | 0.06 | 1480 | 2100 | 5 | ||
PAH3 | NA | 0.7300 | 1.77 | 212.2 | 10 | NA | NA | NA | 0.09 | 1550 | NA | NA | |
SQT | 24.984 | 1.5370 | 1.52 | 273 | 15 | 0.0451 | 346.5 | 0.07 | 1400 | 40 | 380 | ||
TOL1 | 2.326 | 0.0580 | 2.26 | 163 | 6 | 0.0637 | 153.7 | 0.15 | 1240 | 3800 | 2 | ||
TOL2 | 21.277 | 0.1130 | 1.82 | 175 | 8 | 0.0607 | 194.1 | 0.10 | 1240 | 2600 | 4 | ||
TOL3 | NA | 0.300 | 2.70 | 194 | 6 | NA | NA | NA | 0.20 | 1450 | NA | NA | |
TRP1 | 14.792 | 0.1393 | 1.84 | 177 | 8 | 0.0603 | 194.9 | 0.10 | 1400 | 27 | 360 | ||
TRP2 | 133.7297 | 0.4542 | 1.83 | 198 | 9 | 0.0559 | 218.8 | 0.10 | 1400 | 25 | 450 | ||
XYL1 | 1.314 | 0.0310 | 2.42 | 174 | 6 | 0.061 | 154.6 | 0.17 | 1480 | 4900 | 2 | ||
XYL2 | 34.483 | 0.0900 | 1.93 | 185 | 8 | 0.0585 | 194.6 | 0.11 | 1480 | 3100 | 3 | ||
XYL3 | NA | 0.360 | 2.30 | 218 | 8 | NA | NA | NA | 0.15 | 1330 | NA | NA |
. . . . . factor-of-100 increase in MTNO3 Henry's law coefficient, factor-of-10 decrease in , and factor-of-10 decrease in produced better model results in the simulation. See Supplement for a posteriori simulation parameters. NA indicates not applicable (nonvolatile species).
Estimating solubility and deviations from ideality
When deviations from ideality were considered, the saturation concentration used in the modified Raoult's law was adjusted using an activity coefficient. All organic–organic interactions were assumed to be ideal, and only the inclusion of water drove deviation from ideality. Observations during SOAS indicate that despite a factor-of-7 change in ambient aerosol water concentration from night to day, (mole fraction of water in the partitioning medium) typically varied over a narrow range (80 to 96 % by mole) throughout the day. The activity coefficient for each organic species, , was determined using a one-constant Margules equation:
Since (the temperature-dependent constant in the Margules equation) corresponds to the activity coefficient at infinite dilution in water (, it can be estimated based on Henry's law combined with Raoult's law: where is the pure species saturation concentration at . is related to solubility () in mass per volume of water: The saturation concentration as a function of water becomes where is the moles of aerosol water in the partitioning medium. This equation applies across the entire organic-to-water spectrum and shows that represents of a species in water () normalized to the pure species . Evaluating for pure water provides, , the saturation concentration at infinite dilution: Values are available in Table . The solubilities of nonvolatile species derived from traditional precursors (oligomers/accretion products) were estimated based on assuming a between and and the Henry's law coefficients of .
This representation of deviations from ideality resulted in competing effects due to the addition of aerosol water to the partitioning medium. Adding water increased the partitioning medium as described in Sect. , which led to more SOA. However, adding water also increased the activity coefficient via the Margules model (Fig. S2), leading to higher and less favorable partitioning (Fig. S3). The Margules model, combined with the fact that all deviations are observed to be positive for the species examined here, indicated that large additions of water reduced SOA due to the activity coefficient adjustment. Indeed, all saturation concentrations for partitioning into pure water () are higher than those into pure organic () by 1 to 4 orders of magnitude (Table ). A priori assumptions regarding the solubility and activity of monoterpene nitrates were so nonideal that particulate nitrate was driven entirely out of the particle, inconsistent with observations . As a result, the Henry's law coefficient for monoterpene nitrates () was increased by a factor of 100 and all activity coefficients were reduced by a factor of 10 compared to a priori values in the CMAQ simulation. These adjustments, determined through a series of sensitivity simulations, may have been necessary due to inaccuracies in the Henry's law coefficients, effects of inorganics, pure species saturation concentrations, molecular weights, Margules model, or a combination of all of the above. A posteriori parameters used in , which include a factor-of-100 increase in solubility and factor-of-10 decrease in activity coefficients, are available in Table S6.
Estimating WSOC
WSOC is an operationally defined species measured by adding water to a system and analyzing the dissolved compounds . Particulate compounds with solubilities greater than 10 g L tend to be measured as WSOC regardless of the sampling and extraction method, while compounds with solubilities less than g L are insoluble . To determine the fraction of OA extracted as WSOC (), the particle phase can be modeled as an equilibrium between two phases: and . The fraction of species, , in phase compared to the total particulate species concentration is where and are the number of moles in phases and , respectively. If phase has no water and is ideal, while phase is dominated by water and obeys Henry's law, then the fraction of aerosol species extracted as () is where WIOA and LWC are concentration of water-insoluble OA and liquid water in mass per volume of air. Thus WSOC depends on the amount of insoluble material, liquid water, Henry's law coefficient, and pure species saturation concentration.
Observations for evaluation
Simulations were evaluated by comparing to OC from IMPROVE, Chemical Speciation Network (CSN), and SouthEastern Aerosol Research and Characterization (SEARCH) network observations in the eastern US. For comparisons to SEARCH observations, the Jefferson Street, Atlanta, GA (JST), and Birmingham, AL (BHM), urban sites as well as Yorkville, GA (YRK), and CTR, rural sites were considered. In order to estimate secondary organic carbon (SOC), the method of , which uses OC EC (elemental carbon) ratios, was revised to account for the semivolatile nature of POA. For estimating observed POA from total OA only, POA in CMAQ is assumed to correspond to emissions of 3000 and lower-volatility compounds. The volatility distribution of gasoline vehicle POA from and used by the CMAQ-VBS was used to estimate how much POA is expected in the particle under ambient conditions.
The fraction of POA in the particle () for each observation data point was estimated as where the volatility profile is described by one nonvolatile and , 10, 100, and 1000 surrogate species in the following mass-based abundance (): 0.27, 0.15, 0.26, 0.16, and 0.17. Observed SOC was estimated from each observed OC by therefore,
This calculation only accounts for the effect of dilution and partitioning on POC (primary organic carbon) and does not account for chemical processing that may convert POA to SOA. In addition, compared to other volatility profiles such as diesel POA, this profile tends to be weighted toward lower-volatility compounds. As a result, this approach may be an upper bound on the amount of POC (lower bound on SOC).
In addition to the routine monitoring network data, model predictions were compared to data from the CTR ( W, N) and Look Rock, TN (LRK; W, N) sites from the SOAS field campaign in the southeast United States. Observations include water-soluble organic carbon in both particle and gas phase , aerosol LWC , OA , and gas-phase species . The Supplement provides additional evaluation such as a comparison to OH , isoprene , and 2-methyltetrol concentrations.
Results and discussion
Updated base model
Effect of property updates
Figure shows the updated molecular weights as a function of pure species saturation concentration and colored by OM OC. Values are summarized in Table . Four species that were initially outside the O : C and O : C bounds in CMAQ v5.1, ISO1, ISO2, SQT, and BNZ3, were moved within the bounds or just slightly outside as a result of implementing Eq. () through () for traditional OA. The impact of updated OM OC and molecular weight had small impacts on OM (up to 4 % decreases) and larger impacts on OC (5–8 % decrease in OC across the southeast). This change was driven by an increase in the OM OC of biogenic (semivolatile isoprene and monoterpene) SOA.
Note that there is likely inconsistency in the structure and assumed vapor pressure for 2-methyltetrols and 2-methylglyceric acid. The model considers IEPOX-derived SOA to be mainly 2-methyltetrols and organosulfates with a small amount of oligomers . All IEPOX-derived species were treated as nonvolatile, but they should be semivolatile given their molecular weight. Lopez-Hilfiker et al. (2016) indicate that IEPOX-derived organosulfates and 2-methyltetrols measured by common techniques include decomposition products of accretion reactions and that IEPOX-SOA should be relatively nonvolatile, consistent with and the nonvolatile assumption here. The nonvolatile assumption is, however, inconsistent with 2-methyltetrols being present in the gas phase as observed by . The glyoxal SOA in CMAQ also corresponded to a monomeric unit. If oligomers are the dominant form for aqueous methylglyoxal SOA , then the molecular weight would need to be increased. Given the nonvolatile nature of IEPOX-derived SOA and glyoxal SOA, they were not significantly affected by the sensitivity simulations.
In the base and updated models, dry deposition of OA played a relatively minor role in removing semivolatile compounds from the system. Volatility was the primary factor determining the relative role of gas vs. particle deposition for a given species with the specific value of the Henry's law coefficient being less important as indicated by relatively small changes in overall deposition between the base and update (Fig. ). At 298 K, the less volatile SVOCs became more soluble than predicted by base CMAQv5.1, while the more volatile SVOCs became less soluble. With the new parameters, dry deposition of gas-phase SVOCs increased by 20 %, while wet deposition decreased by 6 %. Total SOA+SVOC deposition changed by less than 2 %, and surface concentrations changed by less than 3 %. Overall, particle-phase deposition accounted for 22 % of the loss of SOA+SVOC mass. Dry deposition of gas-phase SVOCs accounted for 32 %, and wet deposition of gas-phase SVOCs accounted for 46 %. The relative role of gas-phase SVOC wet deposition was twice as important as predicted by , consistent with the greater contribution from soluble biogenic species in the southeast in this work. The combined effects of the molecular weight, OM OC, and deposition updates resulted in a 10 % decrease in predicted OC over the southeast.
Contribution of wet (blue) and dry (red) deposition of gas (striped) and particle (solid) SVOCs binned by volatility and overall compared to the base simulation (CMAQ v5.1). Nonvolatile species are indicated by . POA is not included.
[Figure omitted. See PDF]
Isoprene SOA
Heterogeneously derived IEPOX SOA in CMAQ was assumed to be nonvolatile and, thus, was not greatly affected by the sensitivity simulations. Positive matrix factorization (PMF) analysis of Aerosol Chemical Speciation Monitor (ACSM) data and high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) data identified a factor with prominent 82 signals . This factor was referred to as “IEPOX-OA” and “isoprene-OA”, respectively. While it is largely attributed to IEPOX uptake, it may not be entirely due to IEPOX . The term “isoprene-OA” will be used to refer to the ambient PMF factor regardless of technique.
report that only half of the isoprene SOA is from IEPOX in laboratory experiments. Furthermore, the AMS isoprene-OA PMF factor is not fully speciated. During SOAS at the CTR site, were able to explain roughly 50 % of the AMS isoprene-OA at the molecular level. explained 78 % of isoprene-OA at CTR by molecular tracers measured online and identified on filters, but only 26 % of isoprene-OA was linked to tracers at LRK . The lack of mass closure in these studies may have resulted from a lack of authentic standards for quantifying accretion products (oligomers and organosulfates).
Regional modeling also indicates that a number of later-generation species besides IEPOX contribute significantly to isoprene-derived SOA in the United States. indicate that isoprene SOA in the eastern US consists mainly of IEPOX (58 %) and glyoxal (28 %) uptake products, with 14 % due to other species. attribute only 20 % of isoprene-OA to IEPOX uptake, with roughly an equal contribution from methylglyoxal (MGLY) uptake. Semivolatile isoprene SOA and its oligomers accounted for just under 10 % of isoprene SOA in their work. Thus, it is unclear if models can consider only SOA from IEPOX for the isoprene system as a surrogate for AMS-measured isoprene-OA.
Figure shows three model definitions of isoprene-OA: SOA due only to IEPOX-reactive uptake, SOA due to IEPOX-reactive uptake and semivolatile isoprene OH products, and SOA due to IEPOX and glyoxal/methylglyoxal uptake. Also included are the PMF factor observations of isoprene-OA from for CTR and for LRK. SOA is examined relative to sulfate as sulfate provides the acidity and aerosol medium for heterogeneous uptake . Modeled SOA due to IEPOX-reactive uptake was increased relative to CMAQ v5.1 as a result of the higher rate constant for organosulfate formation implemented in this work compared to the work of . At the CTR site, all definitions of isoprene-OA led to overestimates of observed isoprene-OA relative to sulfate. Isoprene-OA based on IEPOX uptake semivolatile Odum two-product surrogates led to the highest predicted concentrations and a slope of 0.70 compared to the observed slope of 0.45. As a result, CMAQ IEPOX-OA could respond more strongly to changes in emissions than ambient data would suggest as the regression coefficient has been interpreted as the magnitude of the sulfate control on isoprene-OA . However, no direct relationship between Odum two-product isoprene SOA and sulfate exists in CMAQ. The correlation between isoprene-OA and sulfate for all three model representations was high () and close to the observed value (), which is also consistent with ongoing modeling work with CMAQv5.1 . On an absolute basis, predicted IEPOX SV (semivolatile) OA reproduced observed isoprene-OA within 6 % overall with small underestimates in the afternoon. However, modeled sulfate concentrations were lower than observed by 30 % and ISOPOOH IEPOX concentrations were overestimated by a factor of 2.4 in the model consistent with other modeling work . Thus, as better agreement is obtained for the gas-phase isoprene species, additional increases in processes that convert isoprene products to the particle phase may be needed despite the overestimates relative to sulfate shown in Figure for Centreville. These additional processes may include accounting for partitioning of 2-methyltetrols to the gas phase, formation of -alkene triols, and/or faster oligomerization .
Isoprene-OA vs. sulfate at (a) CTR and (b) LRK and the slope (b, forced through 0) and correlation coefficient () for each data set. Model representations of isoprene-OA include SOA from IEPOX uptake and semivolatile isoprene OH SOA (IEPOX SV), SOA from IEPOX uptake (IEPOX), and SOA from IEPOX and glyoxal uptake (IEPOX GLY).
[Figure omitted. See PDF]
At LRK, the different model representations of isoprene-OA closely resembled the observed isoprene-OA to sulfate ratio of 0.83. IEPOX uptake alone resulted in a slope of 0.61, and IEPOX uptake along with semivolatile isoprene OH products results in a slope of 0.79. The model showed only a slightly stronger relationship to sulfate than the observations (observed ), with the different model representations indistinguishable in their correlation with sulfate (model to 0.95). Similar to the model at the CTR site, CMAQ underpredicted sulfate at LRK by about 30 %. IEPOX SV isoprene-OA was biased lower than observed isoprene-OA by almost 40 %, and the bias in isoprene-OA (IEPOX SV) was correlated with the bias in sulfate. ISOPOOH IEPOX was underestimated by 60 % at LRK, in contrast to the CTR site, where it was overestimated (Supplement). Thus, isoprene products in the model were too efficiently converted to SOA at LRK despite the low sulfate.
Total OA
Model predictions of OC, SOC, and POC were compared to network observations using the methods described in Sect. to determine how model errors in POA (specifically the nonvolatile assumption) could mask errors in SOA. An IMPROVE network observation with a value of 16.9 (at SHMI1, Shamrock Mine, CO) had a Cook's distance much greater than 1 in a base model–observation comparison and was subsequently removed from all analysis. For the IMPROVE network, 86 % of observed OC was predicted to be secondary in nature (Eq. ), while CMAQ predicted 46 % of OC was secondary. The variability in predicted SOA fraction (standard deviation, , of 0.21) was much higher than the variability in observed SOA fraction (). The CSN network (with a greater proportion of urban sites) was slightly less secondary in nature with 79 % of OC as SOC () and CMAQ predicting 40 % of model OC as SOC (). The SEARCH network was the most influenced by SOA of the three networks. SEARCH OC was predicted to be 88 % SOC (), while CMAQ indicated 58 % SOC (). PMF analysis at the urban JST site during summer 2011 and 2013 indicates that POA (hydrocarbon-like organic aerosol (HOA), biomass burning OA (BBOA), cooking organic aerosol (COA)) factors accounted for 18–30 % of total OA , while CMAQ predicted a 42 % contribution of POC to OC averaged across the urban and rural sites here.
Figure indicates that overestimates in POC roughly compensated for underestimates in SOC in the updated CMAQ model. CMAQ predicted that total OC was within 20 % of average observed OC across each network. The normalized mean bias (NMB) for POC and SOC was much larger in magnitude than for total OC but relatively constant between networks. Specifically, SOC was lower by 40 %, while POC was higher by a factor of 1.7 to 1.8. The overestimate in model POC at the routine network locations was consistent with the model overestimate in AMS/ACSM-measured POA at SOAS CTR and LRK sites. Neither site resolved a HOA-type aerosol , indicating that POA from fossil fuel sources contributed less than 5 % of total OA. A BBOA-type aerosol was resolved at the CTR site and episodic in nature. Comparing CMAQ-predicted POA from all sources to the BBOA factor at CTR indicated that CMAQ generally overestimated POA by a factor of 2, similar to the overestimate for network OC observations.
Aerosol OC, POC, and SOC predicted by the base model simulation () compared to CSN, IMPROVE, and SEARCH (JST, BHM, CTR, and YRK) observations (). Mean bias (MB ) and mean absolute gross error (ME ) are in micrograms of carbon per cubic meter. X symbols indicate mean bias. Boxplots indicate 5th, 25th, median, 75th, and 95th percentile. based on a zero intercept. is the number of observations. NMB .
[Figure omitted. See PDF]
Additional insight into biases can be obtained by examining the diurnal profiles of OC (Fig. ). The diurnal profile of observed OC is relatively flat at the SEARCH sites, consistent with flat total OA . CMAQ predictions had a pronounced diurnal profile, with higher concentrations (and relatively good performance or overpredictions) at night and lower concentrations (coinciding with underestimates) during the day. Averaged across the two urban sites (JST and BHM), however, CMAQ showed no bias as a result of compensating diurnal and spatial errors. Rural OC (YRK and CTR) was underpredicted by about one-third. Also included in Fig. is the diurnal profile of POC in red dashes. Modeled POC at the Atlanta site correctly showed high concentrations in the morning (06:00 LT) and evening (19:00 LT), but tended to peak several hours earlier than HOA observed at JST in 2012 . JST total model-predicted POC during morning and evening transition hours was roughly the same magnitude as total observed OC, further indicating that CMAQ tends to overestimate primary organic aerosol.
OC as a function of hour of the day for a SEARCH urban (Atlanta, JST) and rural (CTR) site during June 2013. Bars/shading indicate 25th to 75th percentiles. Lines indicate means. Red dashed lines indicate model-predicted POC.
[Figure omitted. See PDF]
Role of water
Effect on network OC
Figure shows how including water interactions in absorptive partitioning calculations affected model predictions of OC at routine monitoring network locations. While including water associated with inorganic species (ideal simulation) in the partitioning medium for SOA decreased the bias in SOC for all networks, it led to small increases in the mean error. Except for the SEARCH network, including organic water () also reduced the mean bias at the expense of mean error. The simulation taking into account nonideality () resulted in low normalized mean bias ( 10 %) and large improvements in the mean bias compared to all other simulations. The mean error for was marginally increased over the base simulation.
Bias (model–observation) in SOC for IMPROVE, CSN, and SEARCH networks. SEARCH data are divided into daytime (06:00 to 19:59 LT) and nighttime observations. SOC is calculated using OC EC ratios and estimating evaporation of semivolatiles as described in Sect. . symbols indicate mean bias. Boxplots indicate 5th, 25th, median, 75th, and 95th percentile. based on a zero intercept.
[Figure omitted. See PDF]
Figure highlights that increases in bias occurred during the night (SEARCH network). The largest increases in bias occurred for the simulation as a result of a large contribution of organic water. Similar to the results for the CTR site (Sect. ), daytime concentrations of SOC increased but were still low compared to observations. In general, the variability in the bias increased as a result of water interactions, while the mean bias decreased.
Some caution should be applied when comparing model predictions and observations. Measurements of total aerosol mass from IMPROVE and CSN networks are made under relative humidities of 30–50 %, and quartz filters for OC analysis from IMPROVE may be subject to ambient conditions in the field and during shipping before analysis . Exposure to low RH could cause evaporation of reversible aqueous SOA . have reported that the IMPROVE measurements of OC were 27 % lower than colocated SEARCH measurements during the summer of 2013 and hypothesized the difference to be due to evaporation from the IMPROVE filters during and after sampling. Episodic field campaign observations may be subject to sampling biases as well. Dryers are used ahead of many online aerosol chemistry instruments, and most aerosol water is expected to evaporate in an aerodynamic lens inlet used on many instruments . Such drying can cause changes in the aerosol phase state and could potentially lead to changes in partitioning of soluble organic compounds. have reported a loss of WSOC after drying. Those authors used a post-drying residence time of 7 s, which is much longer than the post-drying time used by the AMS in SOAS (approximately 1 s) and the time in the aerodynamic lens (approximately 0.01 s). A prior study reported that evaporation of ammonium nitrate, a water-soluble and semivolatile species, was not observed when using post-drying residence times of about 1 s . While this topic should be subject to additional research, the AMS data in SOAS are unlikely to have significant biases due to this effect.
Frequency of phase separation
Figure a shows the June 2013 predicted average OM OC across the model domain for the simulation in which phase separation and ideal interactions with inorganic water were predicted (ideal ). Emitted POA in CMAQ has an OM OC of 1.25 for vehicles, 1.7 for biomass burning, and 1.4 for other sources, and heterogeneous aging of the POA results in the OM OC increasing with time . The urban sites of Birmingham, AL, and Atlanta, GA, had predicted OM OC ratios between 1.3 and 2.2 with a mean of 1.8, while the rural SEARCH sites of Centreville, AL, and Yorkville, GA, had values between 1.7 and 2.2 with a mean of 1.9, consistent with previous work .
June 2013 mean predicted (a) OM OC, (b) percentage of time spent separated into organic-rich and inorganic-rich phases, and (c) conditions at CTR-SOAS for the ideal simulation. Separation occurs when RH SRH. Observed RH at SOAS is from the SEARCH network. Panel (c) includes a prediction of time separated using model-predicted RH (solid) and observed RH (dashed).
[Figure omitted. See PDF]
found that particles never undergo phase separation for OM OC above 2.2 (O : C ) and are always phase-separated when OM OC is less than 1.8 (O : C ). Based on Figure b and Eq. (), phase separation was a frequent, but not constant, occurrence. Phase separation was predicted to be more common in urban areas where OM OC was low and near the western portion of the domain where RH was low. Figure c shows RH, SRH, and phase separation for the CTR site. During the day, SRH decreased as a result of increasing OM OC ratios for both SOA and POA. The increase in frequency of separation during the day was driven by low RH values during the day. At CTR, the highest frequency of phase separation was predicted in the late morning. For other sites, separation was more frequent in the afternoon. These results demonstrate the complexity of aerosol phase behavior in the atmosphere, and this complexity impacts the way observations are collected and interpreted.
Model-predicted RH was lower than the observed RH by about 6 % (mean bias). Since phase separation occurred when RH was below the SRH, the frequency of separation using model RH was biased high. In addition, since the model used the SRH predicted for ammonium sulfate, predictions further represent an upper bound on the frequency of phase separation. Thus, particles should be internally mixed without phase separation more often than reported in this work. As phase separation was most consistent with default model assumptions, parameterizing the SRH using data from another salt (and using observed RH) would only increase OA as a result of a greater frequency of inorganic water in the partitioning medium.
Effect of water on OA concentrations at CTR
Figure shows the influence of water on aerosols at the Centreville SOAS site during June 2013. The base simulation underestimated OA overall, but most substantially during the day. Including inorganic water in the partitioning medium when RH SRH (ideal ) resulted in increased OA concentrations at all times of day. Reducing phase separation (under ideal conditions in ideal compared to base) has been shown to increase OA concentrations in box modeling . In CMAQ, concentrations of OA predicted in ideal were 1.5 times higher than observations at night when RH and aerosol liquid water concentrations were highest. Note that nocturnal mixing may be underestimated in the model as indicated by low boundary layer depths, high monoterpene concentrations, and high concentrations compared to observations at night . The simulation considering uptake of water into the organic phase () produced the highest predicted OA concentrations out of all simulations as a result of feedback in the model. Specifically, uptake of water and inclusion in the partitioning medium caused OA concentrations to increase, which further increased the amount of water in the particle and OA. Daytime OA predictions did not exceed observations, but nighttime model concentrations were a factor of 2 higher than observed. A comparison of model-predicted aerosol water with observed aerosol water (Fig. e) indicated that the model overpredicted aerosol LWC by 2–3 at night when interactions were ideal in the simulation.
Observed and predicted concentration of (a) organic aerosol , (b) AMS LO-OOA factor and model-predicted organic-nitrate-derived SOA, (c) OM OC , (d) , (e) aerosol liquid water measured by nephelometer and the Georgia Tech group (solid black) and measured by particle growth and the Rutgers/NC State group (dashed black) , and (f) ratio of predicted to observed quantities influencing organic water () at CTR (for the simulation only). Observed is determined by applying a value of 0.31, 0.20, 0.16, and 0.08 to observed BBOA, isoprene-OA, MO-OOA, and LO-OOA, respectively . Grey shading represents the interquartile range of the observed data (mean in black). Colors represent different simulations in (a)–(e) and different quantities in (f).
[Figure omitted. See PDF]
The simulation accounting for nonideality in addition to phase separation and uptake of water into organic compounds (), produced results similar to the simulation considering phase separation and ideal interactions with inorganic water only (ideal ) in terms of total OA as a function of time of day (model : observation correlation coefficient ; NMB % (), 20 % (ideal )). However, the composition of the aerosol was different. Both simulations in which water interactions were ideal (ideal and ) resulted in overpredictions of less oxidized oxygenated aerosol (LO-OOA) and particle-phase organic nitrates (Supplement). Even with the factor-of-100 increase in Henry's law coefficient for monoterpene nitrates and the factor-of-10 decrease in activity coefficient implemented in compared to a priori estimates, the predicted concentration of organic-nitrate-derived SOA did not substantially change between the base and simulation. The nonideality resulting from including water roughly compensated for the increase in partitioning medium in the case of organic nitrates.
Predicting water uptake onto organic compounds
All simulations indicated that OM OC ratios tend to peak during the day and were near a value of 2, consistent with observations (Fig. c). Semivolatile SOA in the model tended to have lower OM OC ratios than nonvolatile SOA, which resulted in lower OM OC ratios overall in the sensitivity simulations compared to the base. These differences in OM OC between the simulations propagated to predicted values (Fig. d). The base simulation best agreed with the observationally constrained values of , but the model was biased low in all simulations.
Basing the values for organic species on OM OC (or O : C)
may tend to overestimate the values for organic nitrates
. However, good agreement with the LO-OOA factor
Figure e shows two observations of aerosol liquid water content compared to model predictions. In the model, aerosol LWC was represented as the sum of water due to inorganic species (, referred to as inorganic water) and water due to organic species (, referred to as organic water). The ideal and base simulations resulted in the same predictions of aerosol water as only inorganic species were considered in calculating LWC. The difference between the base simulation and observed LWC indicate a potential role for water associated with organic species. The contribution of LWC due to organic species has been estimated as 35 % during SOAS with higher contributions (50 %) at night . Both organic and inorganic water were predicted to be highest in concentration during the night or early morning as a result of the diurnal variation in RH.
Both simulations with uptake of water into organic species ( and ) overpredicted LWC at night, with the simulation resulting in greater overprediction as a result of the feedback mentioned earlier. Figure f attributes the overprediction in organic water for the simulation to errors in the concentration of OA, hygroscopicity parameter for organic aerosol (), and (or RH) (Eq. ). For simplicity in the attribution analysis, RH was converted to activity using a fixed particle diameter of 200 nm . was not directly measured, but estimated using measured properties. Figure f indicates that overestimates in the concentration of OA at night resulted in overestimates in . Underestimates in RH and decreased the overestimate. Thus, predictions of aerosol water in the sensitivity simulations can be most improved by improving the concentration of OA in the model.
The concentration of organic water and contribution to total aerosol water is shown across the model domain in Fig. . was generally predicted to peak in the same locations where OA (Fig. c) was high. This trend was not true in locations where RH drove higher or lower water uptake than expected or OA was dominated by fresh POA with low OM OC. For example, high RH over the Great Lakes and off the northeast coast resulted in high concentrations of organic water. High concentrations of OA from fires in Colorado did not translate to high aerosol water as a result of low RH and low OM OC ratios leading to low . was lower in urban areas as well (near 0.09) due to low OM OC. Regionally, ranged between 0.11 and 0.14. The contribution to aerosol water resulting from organic vs. inorganic species (Fig. b) reflected the ratio of organic-to-sulfate concentrations as aerosol water is proportional to their concentrations.
June 2013 mean predicted (a) aerosol water due to organic species, (b) contribution of organic water to total aerosol water, (c) total organic aerosol, and (d) hygroscopicity parameter for the simulation.
[Figure omitted. See PDF]
Model relationship to WSOC
The Particle-into-Liquid Sampler (PiLS) instrument used to measure
adds an equivalent volume of water of
, which is significantly higher than the concentration
of aerosol water observed during SOAS at CTR
Fraction of OA present in aqueous phase (a) as a function of activity coefficient at infinite dilution and observed OC and at CTR compared to model predictions (b–c). Panel (a) boxplots indicate observed LWC from Rutgers/NC State and Georgia Tech during SOAS. For predictions (a), WIOA is 1 and the species molecular weight is set to 180 g mol. Predictions in dark grey shading span a factor of 2 in WIOA (0.5 to 2 ). Predictions in light grey shading (a) indicate a factor of 10 in WIOA (0.1 to 10 ). Panel (b) corresponds to model predictions in the base simulation, while panel (c) corresponds to predictions in the simulation. Model predictions of OC are stacked and divided into POC, compounds with (solubilities less than 10 g L, Table ), monoterpene nitrate OC, compounds with (solubilities greater than 10 g L), the organic nitrate hydrolysis product, and aqueous SOC.
[Figure omitted. See PDF]
The base simulation provided a good representation of at night but underestimated total OC at all hours of the day, particularly during the daytime. provided a better estimate of total OC but overpredicted at night if compounds with ( g L) were entirely considered WSOC. Recall that the a priori estimate of solubility for was increased by a factor of 100 to reconcile modeled and observed LO-OOA and particulate organic nitrate for . Even with the factor-of-100 increase in Henry's law, remained the least soluble biogenically derived SOA species in the model. The large increase in OC for the nonideal simulation was a result of compounds with solubilities greater than 10 g L or (Fig. c) which were dominated by traditional biogenic SOA and its accretion products. The accretion product from traditional semivolatile SOA is not well constrained in terms of its structure or volatility. In this work, as in the work of and , the species was assumed to be nonvolatile with an OM OC of 2 to 2.1. The solubility of low- monoterpene-derived species remained above 10 g L, even down to species with a saturation concentration of using Henry's law coefficient values from . If the accretion products (AOLGB) were better represented by a less functionalized species and effectively insoluble, observation–model disagreement in in would be reduced. Another way to reconcile observed and modeled may be to take into account deviations from equilibrium during PiLS extraction, which were not considered here.
Figure shows observed water-soluble organic carbon compounds in the gas phase (, measured by mist chamber and total carbon analyzer; ) compared to (a) semivolatile SOA precursors (i.e., those associated with dry organic aerosol in Table 1) and (b) semivolatile and aqueous SOA precursors currently in CMAQ. The figure indicates that considering semivolatile SOA precursors as the only source of in the model underestimated the daytime amount of but that both observed and modeled semivolatile SOA precursors were on the same order of magnitude. Thus, the semivolatile surrogates in the model represented a significant pool of soluble gases. When IEPOX, glyoxal, and methylglyoxal were included in the model estimate of , the daytime was slightly overestimated. However, given the factor of 2.4 overestimate in IEPOX+ISOPOOH in the model compared to observations (Supplement), the speciation of differed in the model and observations. Figure indicates that during the daytime, either additional water-soluble SOA precursors need to be implemented in the model or the model is correct and a significant portion of ambient does not lead to SOA. Indeed, observed may have large contributions from compounds such as formic acid that are not considered significant SOA constituents .
Observed and model SOA precursors considering only semivolatile surrogates (a) and semivolatile and aqueous surrogates (b). Grey shading represents the interquartile range of the observed data (mean in black). Colors represent different simulations.
[Figure omitted. See PDF]
Conclusions
Current chemical transport models consider the dominant pathways to SOA to be dry processes governed by condensation of low-volatility organic compounds in the absence of water. In addition, models generally do not consider uptake of water by organic species. In this work, the CMAQ model was updated to consider aerosol water interactions with semivolatile SOA species and uptake of water into OA with a focus on simulating conditions during the Southern Oxidant and Aerosol Study of 2013. A method ( simulation) was developed to take into account deviations from ideality using an activity coefficient calculated based on the species Henry's law coefficient, pure species saturation concentration (), and the mole fraction of water in the particle that resulted in a normalized mean bias of 4, 10, and 2 % for IMPROVE, CSN, and SEARCH SOC. Monoterpene nitrates were predicted to be the least soluble semivolatile in the model, consistent with SOA yields from -pinene being comparable under dry and humid conditions . However, most biogenic hydrocarbon-derived semivolatile SOA was highly soluble and predicted to be measured as WSOC. Thus, even aerosol formed through dry processes in models may be classified as WSOC as measured by instruments such as the PiLS.
Based on current observations, aerosol water cannot be added to the partitioning medium for semivolatile organic compounds without simultaneously accounting for deviations in ideality. Otherwise, aerosol liquid water and aerosol carbon are overestimated at night. This finding is consistent with the work by , who found that aerosol water concentrations would more than double if ideality was assumed. also found that organic–inorganic water-uptake experiments could not be modeled assuming ideal, well-mixed liquids, and assuming ideality overpredicted -pinene SOA concentrations by 100–200 % in the work of .
All simulations in this work, including the more aggressive ones assuming ideality, could not reproduce daytime observed OA in the southeast US (at SEARCH sites) solely by adding water to the partitioning medium. Including water resulted in increased model error but could reduce the bias in OC. Additional pathways (new precursors and/or new pathways) to OA, particularly during the daytime, are still needed in models.
The updates described here are in three stages of model readiness:
Properties of semivolatile OA constituents can immediately be updated in models to be consistent with their assumed volatility and parent hydrocarbon. Base model performance was good in terms of isoprene-OA and total OC compared to routine networks. Property updates in this work (Table 2) are scheduled for public release as part of CMAQv5.2.
Prediction of organic water is more uncertain, but OM OC is a useful proxy and can be used to parameterize water uptake onto organic species via Eq. () and -Köhler theory.
The effects of water on semivolatile OA partitioning requires additional research as deviations from ideality are important. or are recommended as useful parameters for characterizing solubility. Models such as the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and UManSysProp offer opportunities to perform detailed calculations.
In addition, these areas of model improvement are suggested for future work:
A treatment of semivolatile primary OA is needed to reproduce observed surrogates for POA. Factor-of-2 overestimates in POA were predicted to compensate for underestimates in SOA on the order of 40 % in IMPROVE and CSN networks.
Improvements to sulfate and gas-phase isoprene chemistry will lead to an improved isoprene-OA representation in models as isoprene-OA is correlated with sulfate, but precursors to IEPOX-derived SOA were overestimated at CTR during SOAS. Predictions of isoprene SOA could be further improved by considering the volatility of IEPOX-derived species (such as 2-methyltetrols and -alkene triols) as well as formation of additional species .
Model-predicted aerosol LWC that includes water associated with organic compounds can be most improved by improving the concentration of OA, which may require a number of updates in different areas.
New precursors to SOA are likely needed, especially during the day when OA is underestimated and gas-phase semivolatile model species are less plentiful. Additional precursors for the isoprene system may include multifunctional hydroperoxides .
Code availability
CMAQ is publicly available via github (
Data availability
SOAS field data are available at
The Supplement related to this article is available online at
Acknowledgements
We thank the Computer Sciences Corporation for emission processing and Shaojie Song for GEOS-Chem simulations. We thank Jesse Bash, Donna Schwede, and Matt Woody for useful discussion and Kirk Baker for developing the SOAS modeling platform. We thank William H. Brune, David O. Miller, Philip A. Feiner, and Li Zhang for providing OH data. We thank Paul Wennberg and Tran Nguyen for providing CTR CIMS data for IEPOX ISOPOOH. We thank Rohit Mathur and Golam Sarwar for providing comments on the paper. The US EPA through its Office of Research and Development supported the research described here. It has been subjected to Agency administrative review and approved for publication but may not necessarily reflect official Agency policy. The Ng group was supported by NSF grant 1455588 and EPA grant RD-83540301. Rodney Weber was supported by NSF grant 1242258. Weiwei Hu and Jose L. Jimenez were supported by EPRI 10004734, NSF AGS-1360834, and EPA STAR 83587701-0. Annmarie G. Carlton was supported by EPA STAR grant R83512 and NSF-AGS 1242155. The Surratt group was supported by EPRI as well from EPA grant R835404 and NSF Grant CHE-1404644. The Goldstein team at UC Berkeley acknowledge support from EPA STAR Grant R835407 and NSF Grant AGS-1250569. Gabriel Isaacman-VanWertz is supported by the NSF Graduate Research Fellowship (no. DGE 1106400). Edited by: D. Topping Reviewed by: two anonymous referees
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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
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1 National Exposure Research Laboratory, US Environmental Protection Agency, Research Triangle Park, NC, USA
2 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA
3 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA; School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA
4 Department of Environmental Sciences, Rutgers University, New Brunswick, NJ, USA; now at: Department of Chemistry, University of California, Irvine, CA, USA
5 School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA
6 Gillings School of Global Public Health, The University of North Carolina at Chapel Hill, Chapel Hill, NC, USA
7 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA; School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA; Institute of Environmental Research and Sustainable Development, National Observatory of Athens, Palea Penteli, 15236, Greece; Institute for Chemical Engineering Sciences, Foundation for Research and Technology Hellas, Patras, Greece
8 Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA; Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
9 Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA USA
10 Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA USA; Department of Civil and Environmental Engineering, University of California, Berkeley, CA USA