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Soot and black carbon (BC) particles are generated in the incomplete combustion of fossil fuels, biomass, and biofuels. These airborne particles affect air quality, human health, aerosol–cloud interactions, precipitation formation, and climate. At present, the climate effects of BC particles are not well understood. Their role in cloud formation is obscured by their chemical and physical variability and by the internal mixing states of these particles with other compounds. Ice nucleation in field studies is often difficult to interpret. Nonetheless, most field studies seem to suggest that BC particles are not efficient ice-nucleating particles (INPs). On the other hand, laboratory measurements show that in some cases, BC particles can be highly active INPs under certain conditions. By working with well-characterized BC particles, our aim is to systematically establish the factors that govern the ice nucleation activity of BC. The current study focuses on laboratory measurements of the effectiveness of BC-containing aerosol in the formation of ice crystals in temperature and ice supersaturation conditions relevant to cirrus clouds. We examine ice nucleation on BC particles under water-subsaturated cirrus cloud conditions, commonly understood as deposition-mode ice nucleation. We study a series of well-characterized commercial carbon black particles with varying morphologies and surface chemistries as well as ethylene flame-generated combustion soot. The carbon black particles used in this study are proxies for atmospherically relevant BC aerosols. These samples were characterized by electron microscopy, mass spectrometry, and optical scattering measurements. Ice nucleation activity was systematically examined in temperature and saturation conditions in the ranges of 217≤T≤235 K and 1.0≤Sice≤1.5 and 0.59≤Swater≤0.98, respectively, using a SPectrometer for Ice Nuclei (SPIN) instrument, which is a continuous-flow diffusion chamber coupled with instrumentation to measure light scattering and polarization. To study the effect of coatings on INPs, the BC-containing particles were coated with organic acids found in the atmosphere, namely stearic acid, cis-pinonic acid, and oxalic acid. The results show significant variations in ice nucleation activity as a function of size, morphology, and surface chemistry of the BC particles. The measured ice nucleation activity dependencies on temperature, supersaturation conditions, and the physicochemical properties of the BC particles are consistent with an ice nucleation mechanism of pore condensation followed by freezing. Coatings and surface oxidation modify the initial formation efficiency of pristine ice crystals on BC-containing aerosol. Depending on the BC material and the coating, both inhibition and enhancement in INP activity were observed. Our measurements at low temperatures complement published data and highlight the capability of some BC particles to nucleate ice under low ice supersaturation conditions. These results are expected to help refine theories relating to soot INP activation in the atmosphere.

Optical properties of flame-generated black carbon (BC) containing soot particles were quantified at multiple wavelengths for particles produced using two different flames: a methane diffusion flame and an ethylene premixed flame. Measurements were made for (i) nascent soot particles, (ii) thermally denuded nascent particles, and (iii) particles that were coated and then thermally denuded, leading to the collapse of the initially lacy, fractal-like morphology. The measured mass absorption coefficients (MACs) depended on soot maturity and generation but were similar between flames for similar conditions. For mature soot, here corresponding to particles with volume-equivalent diameters > ∼ 160 nm, the MAC and absorption Ångström exponent (AAE) values were independent of particle collapse while the single-scatter albedo increased. The MAC values for these larger particles were also size-independent. The mean MAC value at 532 nm for larger particles was 9.1±1.1 m2 g−1, about 17 % higher than that recommended by Bond and Bergstrom (2006), and the AAE was close to unity. Effective, theory-specific complex refractive index (RI) values are derived from the observations with two widely used methods: Lorenz–Mie theory and the Rayleigh–Debye–Gans (RDG) approximation. Mie theory systematically underpredicts the observed absorption cross sections at all wavelengths for larger particles (with x > 0.9) independent of the complex RI used, while RDG provides good agreement. (The dimensionless size parameter x = πdp∕λ, where dp is particle diameter and λ is wavelength.) Importantly, this implies that the use of Mie theory within air quality and climate models, as is common, likely leads to underpredictions in the absorption by BC, with the extent of underprediction depending on the assumed BC size distribution and complex RI used. We suggest that it is more appropriate to assume a constant, size-independent (but wavelength-specific) MAC to represent absorption by uncoated BC particles within models.

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH4HSO4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous ice nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.

We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 108 to 2.2 × 1010 molec cm−3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 106 to 2 × 107 molec cm−3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 1011 and 2 × 1011 molec cm−3 s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.

A model has been developed to simulate the formation and evolution of secondary organic aerosol (SOA) and was tested against data produced in a Potential Aerosol Mass (PAM) flow reactor and a large environmental chamber. The model framework is based on the two-dimensional volatility basis set approach (2D-VBS), in which SOA oxidation products in the model are distributed on the 2-D space of effective saturation concentration (Ci*) and oxygen-to-carbon ratio (O : C). The modeled organic aerosol mass concentrations (COA) and O : C agree with laboratory measurements within estimated uncertainties. However, while both measured and modeled O : C increase with increasing OH exposure as expected, the increase of modeled O : C is rapid at low OH exposure and then slows as OH exposure increases while the increase of measured O : C is initially slow and then accelerates as OH exposure increases. A global sensitivity analysis indicates that modeled COA values are most sensitive to the assumed values for the number of Ci* bins, the heterogeneous OH reaction rate coefficient, and the yield of first-generation products. Modeled SOA O : C values are most sensitive to the assumed O : C of first-generation oxidation products, the number of Ci* bins, the heterogeneous OH reaction rate coefficient, and the number of O : C bins. All these sensitivities vary as a function of OH exposure. The sensitivity analysis indicates that the 2D-VBS model framework may require modifications to resolve discrepancies between modeled and measured O : C as a function of OH exposure.

The physical phase state (solid, semi-solid, or liquid) of secondary organic aerosol (SOA) particles has important implications for a number of atmospheric processes. We report the phase state of SOA particles spanning a wide range of oxygen to carbon ratios (O / C), used here as a surrogate for SOA oxidation level, produced in a flow tube reactor by photo-oxidation of various atmospherically relevant surrogate anthropogenic and biogenic volatile organic compounds (VOCs). The phase state of laboratory-generated SOA was determined by the particle bounce behavior after inertial impaction on a polished steel substrate. The measured bounce fraction was evaluated as a function of relative humidity and SOA oxidation level (O / C) measured by an Aerodyne high resolution time of flight aerosol mass spectrometer (HR-ToF AMS). The main findings of the study are: (1) biogenic and anthropogenic SOA particles are found to be amorphous solid or semi-solid based on the measured bounced fraction (BF), which was typically higher than 0.6 on a 0 to 1 scale. A decrease in the BF is observed for most systems after the SOA is exposed to relative humidity of at least 80% RH, corresponding to a RH at impaction of 55%. (2) Long-chain alkanes have a low BF (indicating a "liquid-like", less viscous phase) particles at low oxidation levels (BF < 0.2 ± 0.05 for O / C = 0.1). However, BF increases substantially upon increasing oxidation. (3) Increasing the concentration of sulphuric acid (H2SO4) in solid SOA particles (here tested for longifolene SOA) causes a decrease in BF levels. (4) In the majority of cases the bounce behavior of the various SOA systems did not show correlation with the particle O / C. Rather, the molar mass of the gas-phase VOC precursor showed a positive correlation with the resistance to the RH-induced phase change of the formed SOA particles.

Secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA) were produced in laboratory experiments from the oxidation of fourteen precursors representing atmospherically relevant biogenic and anthropogenic sources. The SOA and OPOA particles were generated via controlled exposure of precursors to OH radicals and/or O3 in a Potential Aerosol Mass (PAM) flow reactor over timescales equivalent to 1–20 days of atmospheric aging. Aerosol mass spectra of SOA and OPOA were measured with an Aerodyne aerosol mass spectrometer (AMS). The fraction of AMS signal at m/z = 43 and m/z = 44 (f43, f44), the hydrogen-to-carbon (H/C) ratio, and the oxygen-to-carbon (O/C) ratio of the SOA and OPOA were obtained, which are commonly used to characterize the level of oxidation of oxygenated organic aerosol (OOA). The results show that PAM-generated SOA and OPOA can reproduce and extend the observed f44–f43 composition beyond that of ambient OOA as measured by an AMS. Van Krevelen diagrams showing H/C ratio as a function of O/C ratio suggest an oxidation mechanism involving formation of carboxylic acids concurrent with fragmentation of carbon-carbon bonds. Cloud condensation nuclei (CCN) activity of PAM-generated SOA and OPOA was measured as a function of OH exposure and characterized as a function of O/C ratio. CCN activity of the SOA and OPOA, which was characterized in the form of the hygroscopicity parameter κorg, ranged from 8.4×10−4 to 0.28 over measured O/C ratios ranging from 0.05 to 1.42. This range of κorg and O/C ratio is significantly wider than has been previously obtained. To first order, the κorg-to-O/C relationship is well represented by a linear function of the form κorg = (0.18±0.04) ×O/C + 0.03, suggesting that a simple, semi-empirical parameterization of OOA hygroscopicity and oxidation level can be defined for use in chemistry and climate models.

We present the first single particle results obtained with an Aerodyne time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The instrument was deployed at the T1 ground site approximately 40 km northeast of the Mexico City Metropolitan Area as part of the MILAGRO field study in March of 2006. The LS-ToF-AMS acquires both ensemble average and single particle data. Over a 75-h sampling period from 27–30 March 2006, 12 853 single particle mass spectra were optically-triggered and saved. The single particles were classified based on observed vaporization histories and measured chemical compositions. The single particle data is shown to provide insights on internal AMS collection efficiencies and ambient mixing state information that augments the ensemble data. Detection of correlated light scattering and chemical ion signals allowed for a detailed examination of the vaporization/ionization process for single particles measured with the AMS instrument. Three particle vaporization event types were identified as a fraction of the total number of particles detected: (1) 23% with prompt vaporization, (2) 26% with delayed vaporization, and (3) 51% characterized as null. Internal consistency checks show that average single particle nonrefractory mass and chemical composition measurements were in reasonable agreement with ensemble measurements and suggest that delayed and null vaporization events are the dominant source of the nonunit collection efficiency of the AMS. Taken together, the simultaneous prompt single particle and aerosol ensemble measurements offer insight into the mixing state and atmospheric transformations of ambient aerosol particles.

Slightly soluble atmospherically relevant organic compounds may influence particle CCN activity and therefore cloud formation. Adipic acid is a frequently employed surrogate for such slightly soluble organic materials. The 11 published experimental studies on the CCN activity of adipic acid particles are not consistent with each other nor do they, in most cases, agree with the Köhler theory. The CCN activity of adipic acid aerosol particles was studied over a significantly wider range of conditions than in any previous single study. The work spans the conditions of the previous studies and also provides alternate methods for producing "wet" (deliquesced solution droplets) and dry adipic acid particles without the need to produce them by atomization of aqueous solutions. The experiments suggest that the scatter in the previously published CCN measurements is most likely due to the difficulty of producing uncontaminated adipic acid particles by atomization of solutions and possibly also due to uncertainties in the calibration of the instruments. The CCN activation of the small (dmdcore≤102 nm), the CCN activity of the coated particles approaches the deliquescence line of adipic acid, suggesting that the total size of the particle determines CCN activation and the soot core acts as a scaffold.

This paper introduces the capability to study simultaneously changes in the density, the chemical composition, the mobility diameter, the aerodynamic diameter, and the layer thickness of multi-layered aerosol particles as they are being altered by heterogeneous chemical reactions. A vaporization-condensation method is used to generate aerosol particles composed of oleic acid outer layers of 2 to 30nm on 101-nm polystyrene latex cores. The layer density is modified by reaction of oleic acid with ozone for variable exposure times. For increasing ozone exposure, the mobility diameter decreases while the vacuum aerodynamic diameter increases, which, for spherical particles, implies that particle density increases. The aerosol particles are confirmed as spherical based upon the small divergence of the particle beam in the aerosol mass spectrometer. The particle and layer densities are calculated by two independent methods, namely one based on the measured aerodynamic and mobility diameters and the other based on the measured mobility diameter and particle mass. The uncertainty estimates for density calculated by the second method are two to three times greater than those of the first method. Both methods indicate that the layer density increases from 0.89 to 1.12g·cm-3 with increasing ozone exposure. Aerosol mass spectrometry shows that, concomitant with the increase in the layer density, the oxygen content of the reacted layer increases. Even after all of the oleic acid has reacted, the layer density and the oxygen content continue to increase slowly with prolonged ozone exposure, a finding which indicates continued chemical reactions of the organic products either with ozone or with themselves. The results of this paper provide new insights into the complex changes occurring for atmospheric particles during the aging processes caused by gas-phase oxidants.