Sensitivity of Aerosol Refractive Index Retrievals Using Optical Spectroscopy

<div><p>Accurate refractive index values are required to determine the effects of aerosol particles on direct radiative forcing. Theoretical retrievals using extinction data alone or extinction plus absorption data have been simulated to determine the sensitivity of each retrieval. A range of aerosol types with a range of different refractive indices were considered. The simulations showed that the extinction-only retrieval was not able to accurately or precisely retrieve refractive index values, even for purely scattering compounds, but the addition of a simulated absorption measurement greatly improved the retrieval.</p><p>Copyright 2014 American Association for Aerosol Research</p></div

Vapor–Wall Deposition in Chambers: Theoretical Considerations

In order to constrain the effects of vapor–wall deposition on measured secondary organic aerosol (SOA) yields in laboratory chambers, researchers recently varied the seed aerosol surface area in toluene oxidation and observed a clear increase in the SOA yield with increasing seed surface area (Zhang, X.; et al. <i>Proc. Natl. Acad. Sci. U.S.A.</i> <b>2014</b>, <i>111</i>, 5802). Using a coupled vapor–particle dynamics model, we examine the extent to which this increase is the result of vapor–wall deposition versus kinetic limitations arising from imperfect accommodation of organic species into the particle phase. We show that a seed surface area dependence of the SOA yield is present only when condensation of vapors onto particles is kinetically limited. The existence of kinetic limitation can be predicted by comparing the characteristic time scales of gas-phase reaction, vapor–wall deposition, and gas–particle equilibration. The gas–particle equilibration time scale depends on the gas–particle accommodation coefficient α_p. Regardless of the extent of kinetic limitation, vapor–wall deposition depresses the SOA yield from that in its absence since vapor molecules that might otherwise condense on particles deposit on the walls. To accurately extrapolate chamber-derived yields to atmospheric conditions, both vapor–wall deposition and kinetic limitations must be taken into account

Heating-Induced Evaporation of Nine Different Secondary Organic Aerosol Types

The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA. This raises questions regarding the use of traditional volatility distributions in the simulation and prediction of atmospheric SOA concentrations. Here, we present results from measurements of thermally induced evaporation of SOA for nine different SOA types (i.e., distinct volatile organic compound and oxidant pairs) encompassing both anthropogenic and biogenic compounds and O₃ and OH to examine the extent to which the low effective volatility of SOA is a general phenomenon or specific to a subset of SOA types. The observed extents of evaporation with temperature were similar for all the SOA types and indicative of a low effective volatility. Furthermore, minimal variations in the composition of all the SOA types upon heating-induced evaporation were observed. These results suggest that oligomer decomposition likely plays a major role in controlling SOA evaporation, and since the SOA formation time scale in these measurements was less than a minute, the oligomer-forming reactions must be similarly rapid. Overall, these results emphasize the importance of accounting for the role of condensed phase reactions in altering the composition of SOA when assessing particle volatility

OH-Initiated Heterogeneous Oxidation of Internally-Mixed Squalane and Secondary Organic Aerosol

Recent work has established that secondary organic aerosol (SOA) can exist as an amorphous solid, leading to various suggestions that the addition of SOA coatings to existing particles will decrease the reactivity of those particles toward common atmospheric oxidants. Experimental evidence suggests that O₃ is unable to physically diffuse through an exterior semisolid or solid layer thus inhibiting reaction with the core. The extent to which this suppression in reactivity occurs for OH has not been established, nor has this been demonstrated specifically for SOA. Here, measurements of the influence of adding a coating of α-pinene+O₃ SOA onto squalane particles on the OH-initiated heterogeneous oxidation rate are reported. The chemical composition of the oxidized internally mixed particles was monitored online using a vacuum ultraviolet-aerosol mass spectrometer. Variations in the squalane oxidation rate with particle composition were quantified by measurement of the effective uptake coefficient, γ_eff, which is the loss rate of a species relative to the oxidant-particle collision rate. Instead of decreasing, the measured γ_eff increased continuously as the SOA coating thickness increased, by a factor of ∼2 for a SOA coating thickness of 42 nm (corresponding to ca. two-thirds of the particle mass). These results indicate that heterogeneous oxidation of ambient aerosol by OH radicals is not inhibited by SOA coatings, and further that condensed phase chemical pathways and rates in organic particles depend importantly on composition

Real-Time Black Carbon Emission Factor Measurements from Light Duty Vehicles

Eight light-duty gasoline low emission vehicles (LEV I) were tested on a Chassis dynamometer using the California Unified Cycle (UC) at the Haagen-Smit vehicle test facility at the California Air Resources Board in El Monte, CA during September 2011. The UC includes a cold start phase followed by a hot stabilized running phase. In addition, a light-duty gasoline LEV vehicle and ultralow emission vehicle (ULEV), and a light-duty diesel passenger vehicle and gasoline direct injection (GDI) vehicle were tested on a constant velocity driving cycle. A variety of instruments with response times ≥0.1 Hz were used to characterize how the emissions of the major particulate matter components varied for the LEVs during a typical driving cycle. This study focuses primarily on emissions of black carbon (BC). These measurements allowed for the determination of BC emission factors throughout the driving cycle, providing insights into the temporal variability of BC emission factors during different phases of a typical driving cycle

Volatility of Primary Organic Aerosol Emitted from Light Duty Gasoline Vehicles

Primary organic aerosol (POA) emitted from light duty gasoline vehicles (LDGVs) exhibits a semivolatile behavior in which heating the aerosol and/or diluting the aerosol leads to partial evaporation of the POA. A single volatility distribution can explain the median evaporation behavior of POA emitted from LDGVs but this approach is unable to capture the full range of measured POA volatility during thermodenuder (TD) experiments conducted at atmospherically relevant concentrations (2–5 μg m^–3). Reanalysis of published TD data combined with analysis of new measurements suggest that POA emitted from gasoline vehicles is composed of two types of POA that have distinctly different volatility distributions: one low-volatility distribution and one medium-volatility distribution. These correspond to fuel combustion-derived POA and motor oil POA, respectively. Models that simultaneously incorporate both of these distributions are able to reproduce experimental results much better (<i>R</i>² = 0.94) than models that use a single average or median distribution (<i>R</i>² = 0.52). These results indicate that some fraction of POA emitted from LDGVs is essentially nonvolatile under typical atmospheric dilution levels. Roughly 50% of the vehicles tested in the current study had POA emissions dominated by fuel combustion products (essentially nonvolatile). Further testing is required to determine appropriate fleet-average emissions rates of the two POA types from LDGVs

The Influence of Molecular Structure and Aerosol Phase on the Heterogeneous Oxidation of Normal and Branched Alkanes by OH

Insights into the influence of molecular structure and thermodynamic phase on the chemical mechanisms of hydroxyl radical-initiated heterogeneous oxidation are obtained by identifying reaction products of submicrometer particles composed of either <i>n</i>-octacosane (C₂₈H₅₈, a linear alkane) or squalane (C₃₀H₆₂, a highly branched alkane) and OH. A common pattern is observed in the positional isomers of octacosanone and octacosanol, with functionalization enhanced toward the end of the molecule. This suggests that relatively large linear alkanes are structured in submicrometer particles such that their ends are oriented toward the surface. For squalane, positional isomers of first-generation ketones and alcohols also form in distinct patterns. Ketones are favored on carbons adjacent to tertiary carbons, while hydroxyl groups are primarily found on tertiary carbons but also tend to form toward the end of the molecule. Some first-generation products, viz., hydroxycarbonyls and diols, contain two oxygen atoms. These results suggest that alkoxy radicals are important intermediates and undergo both intramolecular (isomerization) and intermolecular (chain propagation) hydrogen abstraction reactions. Oxidation products with carbon number less than the parent alkane’s are observed to a much greater extent for squalane than for <i>n</i>-octacosane oxidation and can be explained by the preferential cleavage of bonds involving tertiary carbons

Real-Time Emission Factor Measurements of Isocyanic Acid from Light Duty Gasoline Vehicles

Exposure to gas-phase isocyanic acid (HNCO) has been previously shown to be associated with the development of atherosclerosis, cataracts and rheumatoid arthritis. As such, accurate emission inventories for HNCO are critical for modeling the spatial and temporal distribution of HNCO on a regional and global scale. To date, HNCO emission rates from light duty gasoline vehicles, operated under driving conditions, have not been determined. Here, we present the first measurements of real-time emission factors of isocyanic acid from a fleet of eight light duty gasoline-powered vehicles (LDGVs) tested on a chassis dynamometer using the Unified Driving Cycle (UC) at the California Air Resources Board (CARB) Haagen-Smit test facility, all of which were equipped with three-way catalytic converters. HNCO emissions were observed from all vehicles, in contrast to the idealized laboratory measurements. We report the tested fleet averaged HNCO emission factors, which depend strongly on the phase of the drive cycle; ranging from 0.46 ± 0.13 mg kg_fuel^–1 during engine start to 1.70 ± 1.77 mg kg_fuel^–1 during hard acceleration after the engine and catalytic converter were warm. The tested eight-car fleet average fuel based HNCO emission factor was 0.91 ± 0.58 mg kg_fuel^–1, within the range previously estimated for light duty diesel-powered vehicles (0.21–3.96 mg kg_fuel^–1). Our results suggest that HNCO emissions from LDGVs represent a significant emission source in urban areas that should be accounted for in global and regional models

Parameterized Yields of Semivolatile Products from Isoprene Oxidation under Different NO_<i>x</i> Levels: Impacts of Chemical Aging and Wall-Loss of Reactive Gases

We developed a parametrizable box model to empirically derive the yields of semivolatile products from VOC oxidation using chamber measurements, while explicitly accounting for the multigenerational chemical aging processes (such as the gas-phase fragmentation and functionalization and aerosol-phase oligomerization and photolysis) under different NO_<i>x</i> levels and the loss of particles and gases to chamber walls. Using the oxidation of isoprene as an example, we showed that the assumptions regarding the NO_<i>x</i>-sensitive, multigenerational aging processes of VOC oxidation products have large impacts on the parametrized product yields and SOA formation. We derived sets of semivolatile product yields from isoprene oxidation under different NO_<i>x</i> levels. However, we stress that these product yields must be used in conjunction with the corresponding multigenerational aging schemes in chemical transport models. As more mechanistic insights regarding SOA formation from VOC oxidation emerge, our box model can be expanded to include more explicit chemical aging processes and help ultimately bridge the gap between the process-based understanding of SOA formation from VOC oxidation and the bulk-yield parametrizations used in chemical transport models

Analysis of Organic Anionic Surfactants in Fine and Coarse Fractions of Freshly Emitted Sea Spray Aerosol

The inclusion of organic compounds in freshly emitted sea spray aerosol (SSA) has been shown to be size-dependent, with an increasing organic fraction in smaller particles. Here we have used electrospray ionization-high resolution mass spectrometry in negative ion mode to identify organic compounds in nascent sea spray collected throughout a 25 day mesocosm experiment. Over 280 organic compounds from ten major homologous series were tentatively identified, including saturated (C₈–C₂₄) and unsaturated (C₁₂–C₂₂) fatty acids, fatty acid derivatives (including saturated oxo-fatty acids (C₅–C₁₈) and saturated hydroxy-fatty acids (C₅–C₁₈), organosulfates (C₂–C₇, C₁₂–C₁₇) and sulfonates (C₁₆–C₂₂). During the mesocosm, the distributions of molecules within some homologous series responded to variations among the levels of phytoplankton and bacteria in the seawater. The average molecular weight and carbon preference index of saturated fatty acids significantly decreased within fine SSA during the progression of the mesocosm, which was not observed in coarse SSA, sea-surface microlayer or in fresh seawater. This study helps to define the molecular composition of nascent SSA and biological processes in the ocean relate to SSA composition