Characterization of Aerosol Hygroscopicity Over the Northeast Pacific Ocean: Impacts on Prediction of CCN and Stratocumulus Cloud Droplet Number Concentrations.

During the Marine Aerosol Cloud and Wildfire Study (MACAWS) in June and July of 2018, aerosol composition and cloud condensation nuclei (CCN) properties were measured over the N.E. Pacific to characterize the influence of aerosol hygroscopicity on predictions of ambient CCN and stratocumulus cloud droplet number concentrations (CDNC). Three vertical regions were characterized, corresponding to the marine boundary layer (MBL), an above-cloud organic aerosol layer (AC-OAL), and the free troposphere (FT) above the AC-OAL. The aerosol hygroscopicity parameter (κ) was calculated from CCN measurements (κ CCN) and bulk aerosol mass spectrometer (AMS) measurements (κ AMS). Within the MBL, measured hygroscopicities varied between values typical of both continental environments (~0.2) and remote marine locations (~0.7). For most flights, CCN closure was achieved within 20% in the MBL. For five of the seven flights, assuming a constant aerosol size distribution produced similar or better CCN closure than assuming a constant "marine" hygroscopicity (κ = 0.72). An aerosol-cloud parcel model was used to characterize the sensitivity of predicted stratocumulus CDNC to aerosol hygroscopicity, size distribution properties, and updraft velocity. Average CDNC sensitivity to accumulation mode aerosol hygroscopicity is 39% as large as the sensitivity to the geometric median diameter in this environment. Simulations suggest CDNC sensitivity to hygroscopicity is largest in marine stratocumulus with low updraft velocities (<0.2 m s-1), where accumulation mode particles are most relevant to CDNC, and in marine stratocumulus or cumulus with large updraft velocities (>0.6 m s-1), where hygroscopic properties of the Aitken mode dominate hygroscopicity sensitivity.

Reactive uptake and photo-Fenton oxidation of glycolaldehyde in aerosol liquid water.

The reactive uptake and aqueous oxidation of glycolaldehyde were examined in a photochemical flow reactor using hydrated ammonium sulfate (AS) seed aerosols at RH = 80%. The glycolaldehyde that partitioned into the aerosol liquid water was oxidized via two mechanisms that may produce aqueous OH: hydrogen peroxide photolysis (H2O2 + hν) and the photo-Fenton reaction (Fe (II) + H2O2 + hν). The uptake of 80 (±10) ppb glycolaldehyde produced 2-4 wt % organic aerosol mass in the dark (kH* = (2.09-4.17) × 10(6) M atm(-1)), and the presence of an OH source increased the aqueous uptake by a factor of 4. Although the uptake was similar in both OH-aging mechanisms, photo-Fenton significantly increased the degree of oxidation (O/C = 0.9) of the aerosols compared to H2O2 photolysis (O/C = 0.5). Aerosol organics oxidized by photo-Fenton and H2O2 photolysis resemble ambient "aged" and "fresh" OA, respectively, after the equivalent of 2 h atmospheric aging. No uptake or changes in particle composition occurred on dry seed aerosol. This work illustrates that photo-Fenton chemistry efficiently forms highly oxidized organic mass in aerosol liquid water, providing a possible mechanism to bridge the gap between bulk-phase experiments and ambient particles.

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry.

Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ON-nitrogen appears as NO(x)+ ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using NO(x)+ fragment ratios, organonitrogen ions, HNO(3)+ ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species.

Chemical composition of gas- and aerosol-phase products from the photooxidation of naphthalene.

The current work focuses on the detailed evolution of the chemical composition of both the gas- and aerosol-phase constituents produced from the OH-initiated photooxidation of naphthalene under low- and high-NO(x) conditions. Under high-NO(x) conditions ring-opening products are the primary gas-phase products, suggesting that the mechanism involves dissociation of alkoxy radicals (RO) formed through an RO(2) + NO pathway, or a bicyclic peroxy mechanism. In contrast to the high-NO(x) chemistry, ring-retaining compounds appear to dominate the low-NO(x) gas-phase products owing to the RO(2) + HO(2) pathway. We are able to chemically characterize 53-68% of the secondary organic aerosol (SOA) mass. Atomic oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios measured in bulk samples by high-resolution electrospray ionization time-of-flight mass spectrometry (HR-ESI-TOFMS) are the same as the ratios observed with online high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), suggesting that the chemical compositions and oxidation levels found in the chemically-characterized fraction of the particle phase are representative of the bulk aerosol. Oligomers, organosulfates (R-OSO(3)), and other high-molecular-weight (MW) products are not observed in either the low- or high-NO(x) SOA; however, in the presence of neutral ammonium sulfate seed aerosol, an organic sulfonic acid (R-SO(3)), characterized as hydroxybenzene sulfonic acid, is observed in naphthalene SOA produced under both high- and low-NO(x) conditions. Acidic compounds and organic peroxides are found to account for a large fraction of the chemically characterized high- and low-NO(x) SOA. We propose that the major gas- and aerosol-phase products observed are generated through the formation and further reaction of 2-formylcinnamaldehyde or a bicyclic peroxy intermediate. The chemical similarity between the laboratory SOA and ambient aerosol collected from Birmingham, Alabama (AL) and Pasadena, California (CA) confirm the importance of PAH oxidation in the formation of aerosol within the urban atmosphere.

Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer.

The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photo-oxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of "effective" density of the SOA in the range of 0.64-1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, C02+ ion fragment of oxygenated organics, and higher "delta" values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative "delta" values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in "delta" patterns, is observed in the ozonolysis of alpha-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA.

Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds.

The secondary organic aerosol (SOA) yields from the laboratory chamber ozonolysis of a series of cycloalkenes and related compounds are reported. The aim of this work is to investigate the effect of the structure of the hydrocarbon parent molecule on SOA formation for a homologous set of compounds. Aspects of the compound structures that are varied include the number of carbon atoms present in the cycloalkene ring (C5 to C8), the presence and location of methyl groups, and the presence of an exocyclic or endocyclic double bond. The specific compounds considered here are cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methyl-1-cyclopentene, 1-methyl-1-cyclohexene, 1-methyl-1-cycloheptene, 3-methyl-1-cyclohexene, and methylenecyclohexane. The SOA yield is found to be a function of the number of carbons present in the cycloalkene ring, with an increasing number resulting in increased yield. The yield is enhanced by the presence of a methyl group located at a double-bonded site but reduced by the presence of a methyl group at a non-double-bonded site. The presence of an exocyclic double bond also leads to a reduced yield relative to that of the equivalent methylated cycloalkene. On the basis of these observations, the SOA yield for terpinolene relative to the other cyclic alkenes is qualitatively predicted, and this prediction compares well to measurements of the SOA yield from the ozonolysis of terpinolene. This work shows that relative SOA yields from ozonolysis of cyclic alkenes can be qualitatively predicted from properties of the parent hydrocarbons.

Secondary organic aerosol formation from cyclohexene ozonolysis: effect of OH scavenger and the role of radical chemistry.

To isolate secondary organic aerosol (SOA) formation in ozone-alkene systems from the additional influence of hydroxyl (OH) radicals formed in the gas-phase ozone-alkene reaction, OH scavengers are employed. The detailed chemistry associated with three different scavengers (cyclohexane, 2-butanol, and CO) is studied in relation to the effects of the scavengers on observed SOA yields in the ozone-cyclohexene system. Our results confirm those of Docherty and Ziemann that the OH scavenger plays a role in SOA formation in alkene ozonolysis. The extent and direction of this influence are shown to be dependent on the specific alkene. The main influence of the scavenger arises from its independent production of HO2 radicals, with CO producing the most HO2, 2-butanol an intermediate amount, and cyclohexane the least. This work provides evidence for the central role of acylperoxy radicals in SOA formation from the ozonolysis of alkenes and generally underscores the importance of gas-phase radical chemistry beyond the initial ozone-alkene reaction.

ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon.

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.

State-of-the-art chamber facility for studying atmospheric aerosol chemistry.

A state-of-the-art chamber facility is described for investigation of atmospheric aerosol chemistry. Dual 28 m3 FEP Teflon film chambers are used to simulate atmospheric conditions in which aerosol formation may occur. This facility provides the flexibility to investigate dark, single oxidant reactions as well as full photochemical simulations. This paper discusses the environmental control implemented as well as the gas-phase and aerosol-phase instrumentation used to monitor atmospheric aerosol formation and growth. Physical processes occurring in the chamber and procedures for estimating secondary organic aerosol formation during reaction are described. Aerosol formation and evolution protocols at varying relative humidity conditions are presented.

Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, delta 3-carene-, and cyclohexene-ozone systems.

Atmospheric oxidation of volatile organic compounds can lead to the formation of secondary organic aerosol (SOA) through the gas/particle (G/P) partitioning of the oxidation products. Since water is ubiquitous in the atmosphere, the extent of the partitioning for any individual organic product depends not only on the amounts and properties of the partitioning organic compounds, but also on the amount of water present. Predicting the effects of water on the atmospheric G/P distributions of organic compounds is, therefore, central to understanding SOA formation. The goals of the current work are to gain understanding of how increases in RH affect (1) overall SOA yields, (2) water uptake by SOA, (3) the behaviors of individual oxidation products, and (4) the fundamental physical properties of the SOA phase that govern the G/P distribution of each of the oxidation products. Part 1 of this series considered SOA formation from five parent hydrocarbons in the absence of water. This paper predicts how adding RH to those systems uniformly increases both the amount of condensed organic mass and the amount of liquid water in the SOA phase. The presence of inorganic components is not considered. The effect of increasing RH is predicted to be stronger for SOA produced from cyclohexene as compared to SOA produced from four monoterpenes. This is likely a result of the greater general degree of oxidation (and hydrophilicity) of the cyclohexene products. Good agreement was obtained between predicted SOA yields and laboratory SOA yield data actually obtained in the presence of water. As RH increases, the compounds that play the largest roles in changing both the organic and water masses in the SOA phase are those with vapor pressures that are intermediate between those of essentially nonvolatile and highly volatile species. RH-driven changes in the compound-dependent G/P partitioning coefficient Kp result from changes in both the average molecular weight MWom of the absorbing organic/water phase, and the compound-dependent activity coefficient zeta values. Adding water to the SOA phase by increasing the RH drives down MWom and thereby uniformly favors SOA condensation. The effect of RH on zeta values is compound specific and depends on the hydrophilicity of the specific compound of interest; the more hydrophilic a compound, the more increasing RH will favor its condensation into the SOA phase. The results also indicate that it may be a useful first approximation to assume that zeta = 1 for many compounds making up SOA mixtures.

Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the alpha-pinene/, beta-pinene/, sabinene/, delta3-carene/, and cyclohexane/ozone systems.

Secondary organic aerosol (SOA) forms in the atmosphere when volatile parent compounds are oxidized to form low-volatility products that condense to yield organic particulate matter (PM). Under conditions of intense photochemical smog, from 40 to 80% of the particulate organic carbon can be secondary in origin. Because describing multicomponent condensation requires a compound-by-compound identification and quantification of the condensable compounds, the complexity of ambient SOA has made it difficult to test the ability of existing gas/particle (G/P) partitioning theory to predict SOA formation in urban air. This paper examines that ability using G/P data from past laboratory chamber experiments carried out with five parent hydrocarbons (HCs) (four monoterpenes at 308 K and cyclohexene at 298 K) in which significant fractions (61-100%) of the total mass of SOA formed from those HCs were identified and quantified by compound. The model calculations were based on a matrix representation of the multicomponent, SOA G/P distribution process. The governing equations were solved by an iterative method. Input data forthe model included (i) deltaHC (microg m(-3)), the amount of reacted parent hydrocarbon; (ii) the alpha values that give the total concentration T (gas + particle phase, ng m(-3)) values for each product i according to Ti = 10(3) alphaideltaHC; (iii) estimates of the pure compound liquid vapor pressure pL(degrees) values (at the reaction temperature) for the products; and (iv) UNIFAC parameters for estimating activity coefficients in the SOA phase for the products as a function of SOA composition. The model predicts the total amount Mo (microg m(-3)) of organic aerosol that will form from the reaction of deltaHC, the total aerosol yield Y(= Mo/deltaHC), and the compound-by-compound yield values Yi. An impediment in applying the model is the lack of literature data on PL(degrees) values for the compounds of interest or even on pL(degrees) values for other, similarly low-volatility compounds. This was overcome in part by using the G/P data from the alpha-pinene and cyclohexene experiments to determine pL(degrees) values for use (along with a set of 14 other independent polar compounds) in calculating UNIFAC vapor pressure parameters that were, in turn, used to estimate all of the needed pL(degrees) values. The significant degree of resultant circularity in the calculations for alpha-pinene and cyclohexene helped lead to the good agreement that was found between the Yi values predicted by the model, and those measured experimentally for those two compounds. However, the model was also able to predict the aerosol yield values from beta-pinene, sabinene, and delta3-carene, for which there was significatly less circularity in the calculations, thereby providing evidence supporting the idea that given the correct input information, SOA formation can in fact be accurately modeled as a multicomponent condensation process.

Sampling atmospheric carbonaceous aerosols using a particle trap impactor/denuder sampler.

A particle trap impactor/denuder system has been developed and tested for the sampling of ambient carbonaceous aerosols. Use of a particle trap impactor allows for a reduction of particle bounce and re-entrainment at high particle loadings, and operation at high volumetric flow rates is achieved without the use of oiled impaction substrates, thus facilitating the chemical and physical analysis of the organic compounds comprising the collected gas (G) and particle (P) phases. Honeycomb denuders have a greater density of channels for a given denuder cross-sectional area than parallel plate or annular denuders; for a given sampling flow rate, honeycomb denuders can be fabricated in more compact shapes and will have a greater amount of surface area for the collection of gases. Field testing of the sampler was conducted primarily at night to minimize the evaporation of organic carbon (OC) from collected particles, which can result from the heating of collected particles as ambient temperatures rise during the day. In side-by-side testing with an open-face filter pack sampler, the denuder system was found to minimize positive gas adsorption artifacts caused by the adsorption of gaseous OC to quartz filter fiber (QFF) surfaces. In the denuder sampler, negligible amounts of OC were observed on a QFF placed downstream of a particle-loaded QFF, suggesting that OC detected on the backup QFF in the filter pack sampler resulted primarily from the adsorption of ambient G-phase OC rather than OC evaporated from particles collected on the front filter. Equations are presented for the evaluation of the magnitude of positive and negative sampling artifacts. Analysis of these equations indicates that the mass of OC evaporated from filter-bound particles present downstream of a denuder depends on (i) the volume of OC-free gas passed through the filter, (ii) the P-phase concentration and the P/G partition coefficients (Kp) of the compounds comprising the P-phase OC, (iii) the temperature (T) (values of Kp are inversely proportional to T), and (iv) the mass fraction of carbon in the compounds comprising P-phase OC. For these reasons, the magnitude of evaporative losses of OC in denuder samplers may vary among different sampling events. In addition, a method utilizing gas chromatography/mass spectrometry has been developed for determination of inertial impactor collection efficiency and denuder particle transmission efficiency. Using this method, only a single extraction of the sampler components is necessary, thereby reducing the number of extractions and analyses over conventional approaches by at least a factor of 2.

The use of ambient measurements to identify which precursor species limit aerosol nitrate formation.

A thermodynamic equilibrium model was used to investigate the response of aerosol NO3 to changes in concentrations of HNO3, NH3, and H2SO4. Over a range of temperatures and relative humidities (RHs), two parameters provided sufficient information for indicating the qualitative response of aerosol NO3. The first was the excess of aerosol NH4+ plus gas-phase NH3 over the sum of HNO3, particulate NO3, and particulate SO4(2-) concentrations. The second was the ratio of particulate to total NO3 concentrations. Computation of these quantities from ambient measurements provides a means to rapidly analyze large numbers of samples and identify cases in which inorganic aerosol NO3 formation is limited by the availability of NH3. Example calculations are presented using data from three field studies. The predictions of the indicator variables and the equilibrium model are compared.

The atmospheric aerosol-forming potential of whole gasoline vapor.

A series of sunlight-irradiated, smog-chamber experiments confirmed that the atmospheric organic aerosol formation potential of whole gasoline vapor cna be accounted for solely in terms of the aromatic fraction of the fuel. The total amount of secondary organic aerosol produced from the atmospheric oxidation of whole gasoline vapor can be represented as the sum of the contributions of the individual aromatic molecular constituents of the fuel. The urban atmospheric, anthropogenic hydrocarbon profile is approximated well by evaporated whole gasoline, and thus these results suggest that it is possible to model atmospheric secondary organic aerosol formation.

Achieving acceptable air quality: some reflections on controlling vehicle emissions.

Motor vehicle emissions have been and are being controlled in an effort to abate urban air pollution. This article addresses the question: Will the vehicle exhaust emission control and fuel requirements in the 1990 Clean Air Act Amendments and the California Air Resources Board regulations on vehicles and fuels have a significant impact? The effective control of in-use vehicle emissions is the key to a solution to the motor vehicle part of the urban air pollution problem for the next decade or so. It is not necessary, except perhaps in Southern California, to implement extremely low new car emission standards before the end of the 20th century. Some of the proposed gasoline volatility and composition changes in reformulated gasoline will produce significant reductions in vehicle emissions (for example, reduced vapor pressure, sulfur, and light olefin and improved high end volatility), whereas others (such as substantial oxygenate addition and aromatics reduction) will not.

Resonance structures in elastic and Raman scattering from microspheres.

To study the interactions between Mie scattering and Raman emissions of spherical particles, we measured the Raman spectra together with the elastically scattered light of the excitation source of an evaporating aqueous sodium nitrate droplet. Resonance structures were observed in the temporal profiles of the elastically scattered light and Raman nitrate and water emissions. The resonance structures in these three profiles occurred in a concerted mode but sometimes occurred independently of each other. A model of inelastic scattering by microspheres by Kerker et al. ["Raman and Fluorescent Scattering by Molecules Embedded in Spheres with Radii up to Several Multiples of the Wavelength," Appl. Opt. 18, 1172-1179 (1979); "Lorenz-Mie Scattering by Spheres: Some Newly Recognized Phenomena," Aerosol Sci. Technol. 1, 275-291 (1982); "Inelastic Light Scattering," in Aerosol Microphysics I: Particle Interaction, W. H. Marlow, Ed. (Springer-Verlag, New York, 1980); "Model for Raman and Fluorescent Scattering by Molecules Embedded in Small Particles," Phys. Rev. A 13, 396-404 (1976)] and the behavior of low order Mie resonances were used to explain the data. This type of data can be used for the determination of chemical compositions of spherical particles.

Urban air pollution: state of the science.

Urban air pollution is comprised of a highly complex mixture of gaseous and particulate components. Much progress has been made in our understanding of the detailed chemistry and physics of air pollution, but important areas of uncertainty still remain.