Search

Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low- NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78% of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m=z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O D C5H6O+=OA) across multiple field, chamber, and source data sets. A background of ~1.7±0.1% (%Dparts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1±0.6% are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5±2.0 %) is 4 times lower than the average for IEPOX-SOA (22±7 %), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~6.5±2.2% on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 %) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (<3 %) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m=z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOXSOA and will enable improved characterization of this OA component. [ABSTRACT FROM AUTHOR]

The change in shape of atmospherically relevant organic particles is used to estimate the viscosity of the particle material without the need for removal from aerosol suspension. The dynamic shape factors X of particles produced by α-pinene ozonolysis in a flow tube reactor, under conditions of particle coagulation, were measured while altering the relative humidity (RH) downstream of the flow tube. As relative humidity was increased, the results showed that X could change from 1.27 to 1.02, corresponding to a transition from aspherical to nearly spherical shapes. The shape change could occur at elevated RH because the organic material had decreased viscosity and was therefore able to flow to form spherical shapes, as favored by the minimization of surface area. Numerical modeling was used to estimate the particle viscosity associated with this flow. Based on particle diameter and RH exposure time, the viscosity dropped from 10(8.7±2.0) to 10(7.0±2.0) Pa s (two sigma) for an increase in RH from <5 to 58% at 293 K. These results imply that the equilibration of the chemical composition of the particle phase with the gas phase can shift from hours at mid-range RH to days at low RH. [ABSTRACT FROM AUTHOR]

Real-time mass spectra of the non-refractory species in submicron aerosol particles were recorded in a tropical rainforest in the central Amazon Basin during the wet season from February to March 2008, as a part of the Amazonian Aerosol Characterization Experiment (AMAZE- 08). Organic material accounted on average for more than 80% of the non-refractory submicron particle mass concentrations during the period of measurements. There was insufficient ammonium to neutralize sulfate. In this acidic, isoprene-rich, HO2-dominant environment, positive-matrix factorization of the time series of particle mass spectra identified four statistical factors to account for the 99% of the variance in the signal intensities of the organic constituents. The first factor was identified as associated with regional and local pollution and labeled "HOA" for its hydrocarbon-like characteristics. A second factor was associated with longrange transport and labeled "OOA-1" for its oxygenated characteristics. A third factor, labeled "OOA-2," was implicated as associated with the reactive uptake of isoprene oxidation products, especially of epoxydiols to acidic haze, fog, or cloud droplets. A fourth factor, labeled "OOA-3," was consistent with an association with the fresh production of secondary organic material (SOM) by the mechanism of gasphase oxidation of biogenic volatile organic precursors followed by gas-to-particle conversion of the oxidation products. The suffixes 1, 2, and 3 on the OOA labels signify ordinal ranking with respect to the extent of oxidation represented by the factor. The process of aqueous-phase oxidation of water-soluble products of gas-phase photochemistry might also have been associated to some extent with the OOA-2 factor. The campaign-average factor loadings had a ratio of 1:4 V 1 for OOA-2 VOOA-3, suggesting the comparable importance of particle-phase compared to gas-phase pathways for the production of SOM during the study period. [ABSTRACT FROM AUTHOR]

The change in shape of atmospherically relevant organic particles is used to estimate the viscosity of the particle material without the need for removal from aerosol suspension. The dynamic shape factors Χ of particles produced by α-pinene ozonolysis in a flow tube reactor, under conditions of particle coagulation, were measured while altering the relative humidity (RH) downstream of the flow tube. As relative humidity was increased, the results showed that Χ could change from 1.27 to 1.02, corresponding to a transition from aspherical to nearly spherical shapes. The shape change could occur at elevated RH because the organic material had decreased viscosity and was therefore able to flow to form spherical shapes, as favored by minimization of surface area. Numerical modeling was used to estimate the particle viscosity associated with this flow. Based on particle diameter and RH exposure time, the viscosity dropped from 10(8.7±2.0) to 10(7.0±2.0) Pa s (2σ) for an increase in RH from < 5 to 58% at 293 K, corresponding to a solid to semisolid transition for the organic material. These results imply that the equilibration of the chemical composition of the particle phase with the gas phase can shift from hours at mid-range RH to weeks for low RH. [ABSTRACT FROM AUTHOR]

The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN) was examined as a function of oxygen-to-carbon elemental ratio (O : C). New data were collected for adipic, pimelic, suberic, azelaic, and pinonic acids. Secondary organic materials (SOMs) produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O:C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] >0.6, 0.2 <[O : C] <0.6, and [O : C] <0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O :C = 0.69-0.72) and α-pinene-derived SOM (O :C=0.38-0.48). Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O: C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O: C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the difference in the behavior of α-pinene-derived SOM compared to that of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e., insoluble regime) whereas those dominated by oxygenated organic components activate (i.e., highly soluble regime) for typical atmospheric cloud life cycles. [ABSTRACT FROM AUTHOR]

The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN) was examined as a function of oxygen-to-carbon elemental ratio (O:C). New data were collected for adipic, pimelic, suberic, azelaic and pinonic acids. Secondary organic materials (SOMs) produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O: C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] > 0.6, 0.2 < [O : C] < 0.6, and [O : C] < 0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O:C = 0.69-0.72) and α-pinene-derived SOM (O: C = 0.38-0.48). Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O: C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O: C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the differences of α-pinene-derived SOM compared to the behavior of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e. insoluble regime) whereas those dominated by oxygenated organic components activate (i.e. highly soluble regime). [ABSTRACT FROM AUTHOR]

The influence of second-generation products on the particle mass yield of β-caryophyllene ozonolysis was systematically tested and quantified. The approach was to vary the relative concentrations of first- and second-generation products by controlling ozone concentration, while observing the change in particle mass yield. For all organic particle mass concentrations Morg of this study (0.5 < Morg < 230 µgm-3), the data show that particle-phase organic material was in large part composed of second-generation products. For 0.5 < Morg < 10 µg m-3, a range which overlaps with atmospheric concentrations, the particle mass yield was not sensitive to ozone exposure, implying that the constituent molecules were rapidly produced at all investigated ozone exposures. In contrast, for Morg > 10 µg m-3 the particle mass yield increased with ozone exposure. These different dependencies on ozone exposure with Morg are explained by a combination of the ozonolysis lifetimes of the first- generation products and the volatility distribution of the resulting second-generation products. First-generation products that have short lifetimes produce low-volatility second-generation products whereas first-generation products that have long lifetimes produce high-volatility second-generation products. The ultimate particle mass yield was defined by mass-based stoichiometric yields α0 = 0.17 ± 0.05, α1 = 0.11 ± 0.17, and α2 = 1.03 ± 0.30 for corresponding saturation concentrations of 1, 10, and 100 µg m-3. Terms α0 and α1 had low sensitivity to the investigated range of ozone exposure whereas term α2 increased from 0.32 ± 0.13 to 1.03 ± 0.30 as the ozone exposure was increased. These findings potentially allow for simplified yet nevertheless accurate parameterizations in air quality and climate models that seek to represent the ozonolysis particle mass yield of certain classes of biogenic compounds. [ABSTRACT FROM AUTHOR]

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. CCN properties were measured and characterized during the CAREBeijing-2006 campaign at a regional site south of the megacity of Beijing, China. Size-resolved CCN efficiency spectra recorded for a supersaturation range of S =0.07% to 0.86% yielded average activation diameters in the range of 190 nm to 45 nm. The corresponding effective hygroscopicity parameters (κ) exhibited a strong size dependence ranging from ~0.25 in the Aitken size range to ~0.45 in the accumulation size range. The campaign average value (κ = 0.3±0.1) was similar to the values observed and modeled for other populated continental regions. The hygroscopicity parameters derived from the CCN measurements were consistent with chemical composition data recorded by an aerosol mass spectrometer (AMS) and thermo-optical measurements of apparent elemental and organic carbon (EC and OC). The CCN hygroscopicity and its size dependence could be parameterized as a function of only AMS based organic and inorganic mass fractions (forg, finorg) using the simple mixing rule κp ≈ 0.1 ⋅ forg +0.7 ⋅ finorg. When the measured air masses originated from the north and passed rapidly over the center of Beijing (fresh city pollution), the average particle hygroscopicity was reduced (κ = 0.2±0.1), which is consistent with enhanced mass fractions of organic compounds (~50 %) and EC (~30 %) in the fine particulate matter (PM1). Moreover, substantial fractions of externally mixed weakly CCN-active particles were observed at low supersaturation (S =0.07 %), which can be explained by the presence of freshly emitted soot particles with very low hygroscopicity (κ <0.1). Particles in stagnant air from the industrialized region south of Beijing (aged regional pollution) were on average larger and more hygroscopic, which is consistent with enhanced mass fractions (~60 %) of soluble inorganic ions (mostly sulfate, ammonium, and nitrate). Accordingly, the number concentration of CCN in aged air from the megacity region was higher than in fresh city out- flow ((2.5-9.9)x10³ cm-3 vs. (0.4-8.3)x10³ cm-3 for S = 0.07-0.86 %) although the total aerosol particle number concentration was lower (1.2x104 cm-3 vs. 2.3x104 cm-3). A comparison with related studies suggests that the fresh outflow from Chinese urban centers generally may contain more, but smaller and less hygroscopic aerosol particles and thus fewer CCN than the aged outflow from megacity regions. [ABSTRACT FROM AUTHOR]

Individual particles that on a mass basis consist dominantly of the components ammonium sulfate, oxygenated organic material, and water are a common class of submicron particles found in today's atmosphere. Here we use (1) the organic-to-sulfate (org:sulf) mass ratio of the overall particle and (2) the oxygen-to-carbon (O:C) elemental ratio of the organic component as input variables in parameterisations that predict the critical relative humidity of several different types of particle phase transitions. Specifically these variables were used to predict the critical relative humidity of liquid-liquid phase separation (SRH), efflorescence (ERH), and deliquescence (DRH). Experiments were conducted by optical microscopy for 11 different oxygenated organic-ammonium sulfate systems covering the range 0.1

Individual particles that on a mass basis consist dominantly of the components ammonium sulfate, organic material, and water are a common class of submicron particles found in today's atmosphere. Here we use (1) the organic-to-sulfate (org:sulf) mass ratio of the overall particle and (2) the oxygen-to-carbon (O:C) elemental ratio of the organic component as input variables in parameterisations that predict the critical relative humidity of several different types of particle phase transitions. These transitions include liquid-liquid phase separation (SRH), efflorescence (ERH), and deliquescence (DRH). Experiments were conducted by optical microscopy for 11 different oxygenated organic-ammonium sulfate systems covering the range 0.1 < org:sulf < 12.8 and 0.29 < O:C < 1.33. These new data, in conjunction with other data already available in the literature, were used to develop the parameterisations SRH(org:sulf, O:C), ERH(org:sulf, O:C), and DRH(org:sulf, O:C). The parameterisations correctly predicted SRH within 15% RH for 86% of the measurements, ERH within 5% for 86% of the measurements, and DRH within 5% for 95% of the measurements. The applicability of the derived parameterisations beyond the training data set was tested against observations for organic-sulfate particles produced in an environmental chamber. The organic component consisted of secondary organic material produced by the oxidation of isoprene, α-pinene, and β-caryophyllene. The predictions of the parameterisations were also tested against data from the Southern Great Plains, Oklahoma, USA. The observed ERH and DRH values for both the chamber and field data agreed within 5% RH with the value predicted by the parameterisations using the measured org:sulf and O:C ratios as the input variables. [ABSTRACT FROM AUTHOR]

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. CCN properties were measured and characterized during the CAREBeijing-2006 campaign at a regional site south of the megacity of Beijing, China. Size-resolved CCN efficiency spectra recorded for a supersaturation range of S = 0.07% to 0.86% yielded average activation diameters in the range of 190 nm to 45 nm. The corresponding effective hygroscopicity parameters (Κ) exhibited a strong size dependence ranging from ~0.25 in the Aitken size range to ~0.45 in the accumulation size range. The campaign average value (Κ = 0.3 ± 0.1) was similar to the values observed and modeled for other populated continental regions. The hygroscopicity parameters derived from the CCN measurements were consistent with chemical composition data recorded by an aerosol mass spectrometer (AMS) and thermo-optical measurements of apparent elemental and organic carbon (ECa and OC). The CCN hygroscopicity and its size dependence could be parameterized as a function of AMS based organic and inorganic mass fractions using the simple mixing rule Κ ≈ 0.1 · forg + 0.7 · finorg. When the measured air masses originated from the north and passed rapidly over the center of Beijing (fresh city pollution), the average particle hygroscopicity was reduced (Κ = 0.2 ± 0.1), which is consistent with enhanced mass fractions of organic compounds (~50%) and ECa (~30%) in the fine particulate matter (PM ). Moreover, substantial fractions of externally mixed weakly CCN-active particles were observed at low supersaturation (S = 0.07%), which can be explained by the presence of freshly emitted soot particles with very low hygroscopicity (Κ < 0.1). Particles in stagnant air from the industrialized region south of Beijing (aged regional pollution) were on average larger and more hygroscopic, which is consistent with enhanced mass fractions (~60%) of soluble inorganic ions (mostly sulfate, ammonium, and nitrate). Accordingly, the number concentration of CCN in aged air from the megacity region was higher than in fresh city outflow ((2.5-9.9)×10³ cm-3 vs. (0.4-8.3)×10³ cm-3) although the total aerosol particle number concentration was lower (1.2×104 cm-3 vs. 2.3×104 cm-3). A comparison with related studies suggests that the fresh outflow from Chinese urban centers generally may contain more, but smaller and less hygroscopic aerosol particles and thus fewer CCN than the aged outflow from megacity regions. [ABSTRACT FROM AUTHOR]

We measured the mobility equivalent critical dry diameter for cloud condensation nuclei (CCN) activation (dc_me) and the particle mass of size-selected (NH4)2SO4 and NaCl particles to calibrate a CCN counter (CCNC) precisely. The CCNC was operated downstream of a differential mobility analyzer (DMA) for the measurement of dc_me. The particle mass was measured using an aerosol particle mass analyzer (APM) operated downstream of the DMA. The measurement of particle mass was conducted for 50-150-nm particles. Effective densities (ρeff) of (NH4)2SO4 particles were 1.67-1.75 g cm-3, which correspond to dynamic shape factors (χ) of 1.01-1.04. This shows that (NH4)2SO4 particles are not completely spherical. In the case of NaCl particles, ρeff was 1.75-1.99 g cm-3 and χ was 1.05-1.14, demonstrating that the particle shape was non-spherical. Using these experimental data, the volume equivalent critical dry diameter (dc_ve) was calculated, and it was used as an input parameter for calculations of critical supersaturation (S). Several thermodynamics models were used for the calculation of water activity. When the Pitzer model was employed for the calculations, the critical S calculated for (NH4)2SO4 and NaCl agreed to well within the uncertainty of 2% (relative). This result demonstrates that the use of the Pitzer model for the calibration of CCNCs gives the most accurate value of S. [ABSTRACT FROM AUTHOR]

We measured the mobility equivalent critical dry diameter for CCN activation (dc_me) and the particle mass of size-selected (NH4)2SO4 and NaCl particles to calibrate a CCN counter (CCNC) precisely. The CCNC was operated downstream of a differential mobility analyzer (DMA) for the measurement of dc_me. The particle mass was measured using an aerosol particle mass analyzer (APM) operated downstream of the DMA. The measurement of particle mass was conducted for 50-150-nm particles. Effective densities (ρeff) of (NH4)2SO4 particles were 1.67-1.75 g cm-3, which correspond to the dynamic shape factors (χ) of 1.01-1.04. This shows that (NH4)2SO4 particles are not completely spherical. In the case of NaCl particles, ρeff was 1.75-1.99 g cm-3 and χ was 1.05-1.14, demonstrating that their particle shape was nonspherical. Using these experimental data, the volume equivalent critical dry diameter (dc_ve) was calculated, and it was used as an input parameter for calculations of critical supersaturation (S). Several thermodynamics models were used for the calculation of water activity. When the Pitzer model was employed for the calculations, the critical S calculated for (NH4)2SO4 and NaCl agreed to well within the uncertainty of 2% (relative). This result demonstrates that the use of the Pitzer model for the calibration of CCNCs gives the most probable value of S. [ABSTRACT FROM AUTHOR]

We measured the number concentrations of cloud condensation nuclei (CCN) and the size distributions of CCN/CN (CN: condensation nuclei) ratios at supersaturations (SSs) of 0.097, 0.27, 0.58, and 0.97% at Jeju Island, Korea during March-April 2005. We made simultaneous measurements of aerosol inorganic ions, water-soluble organic carbon (WSOC), organic carbon (OC), and elemental carbon (EC) in PM2.5. The CCN/CN ratios increased with increasing particle diameter, and the diameter at CCN/CN=0.5 was defined as D50. D50 represents the activation dry diameter of atmospheric particles. The average D50 at SS=0.097% and 0.97% was 136±17 nm and 31±3 nm, respectively. The temporal variation of D50 at SS=0.097% was correlated with the mass fraction of water-soluble components (inorganic ions + WSOC), indicating that the temporal variation of CCN activity was mainly controlled by changes in the water-soluble components fraction. The critical dry diameter (Dcrit), which is the threshold dry diameter for CCN activation, was calculated from the observed aerosol chemical compositions by Köhler theory for comparison with D50. The D50 at SS=0.097% was correlated (r²=0.48) with calculated Dcrit, although Dcrit was larger than D50 by 20-29% on average. The systematic difference between D50 and Dcrit could be caused by the size dependence of the aerosol chemical compositions or surface tension lowering caused by the mixing of water-soluble organic compounds. This difference corresponds to a 27²14% uncertainty in the CCN number concentration estimated from the observed particle number size distribution. [ABSTRACT FROM AUTHOR]

We measured the number concentrations of cloud condensation nuclei (CCN) and the size distributions of CCN/CN (CN: condensation nuclei) ratios at supersaturations (SSs) of 0.097, 0.27, 0.58, and 0.97% at Jeju-Island, Korea during March-April 2005. Measurements of aerosol inorganic ions, water-soluble organic carbon (WSOC), organic carbon (OC), and elemental carbon (EC) in PM2.5 were simultaneously made. The CCN/CN ratios increased with increasing particle diameter, and the diameter at CCN/CN=0.5 was defined as D50. D50 represents the activation dry diameter of atmospheric particles. The average D50 at SS=0.097% and 0.97% was 136 nm and 31 nm, respectively. The temporal variation of D50 at SS=0.097% was correlated with the mass fraction of water-soluble components (inorganic ions + WSOC), indicating that the temporal variation of CCN activity was mainly controlled by changes in the water-soluble components fraction. The critical dry diameter (Dcrit), which is the threshold dry diameter for CCN activation, was calculated from the observed aerosol chemical com positions by Köhler theory for comparison with D50. The D50 at SS=0.097% was correlated (r²=0.48) with calculated Dcrit, although Dcrit were larger than D50 by 20-29% on average. The systematic difference between D50 and Dcrit could be caused by the size dependence of the aerosol chemical compositions or surface tension lowering caused by the mixing of water-soluble organic compounds. This difference corresponds to a 27±14% uncertainty in the CCN number concentration estimated from the observed particle number size distribution. [ABSTRACT FROM AUTHOR]