Volatility and Aging of Atmospheric Organic Aerosol

Donahue, Neil M.; Robinson, Allen L.; Trump, Erica R.; Riipinen, Ilona; Kroll, J. H.

doi:10.1007/128_2012_355

Cited by 96 publications

(98 citation statements)

References 194 publications

(261 reference statements)

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“…SOA is exposed to complex heterogeneous and condensedphase aging processes such as oxidation by hydroxyl radicals (OH) and ozonolysis. Through these processes, SOA may form intricate mixtures of potentially highly functionalized constituents with varying volatility and hygroscopicity known to comprise a substantial fraction of semivolatile organic compounds (SVOCs; Jimenez et al, 2009;Donahue et al, 2014). The finding that atmospheric SOA can take on a highly viscous, semi-solid or even glassy state has drawn attention to its physical state and how low humidity and temperature facilitate glass formation (Zobrist et al, 2008;Murray, 2008;Virtanen et al, 2010;Koop et al, 2011;Bateman et al, 2015Bateman et al, , 2016.…”

Section: Introductionmentioning

confidence: 99%

Diffusivity measurements of volatile organics in levitated viscous aerosol particles

et al. 2017

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Abstract. Field measurements indicating that atmospheric secondary organic aerosol (SOA) particles can be present in a highly viscous, glassy state have spurred numerous studies addressing low diffusivities of water in glassy aerosols. The focus of these studies is on kinetic limitations of hygroscopic growth and the plasticizing effect of water. In contrast, much less is known about diffusion limitations of organic molecules and oxidants in viscous matrices. These may affect atmospheric chemistry and gas-particle partitioning of complex mixtures with constituents of different volatility. In this study, we quantify the diffusivity of a volatile organic in a viscous matrix. Evaporation of single particles generated from an aqueous solution of sucrose and small amounts of volatile tetraethylene glycol (PEG-4) is investigated in an electrodynamic balance at controlled relative humidity (RH) and temperature. The evaporative loss of PEG-4 as determined by Mie resonance spectroscopy is used in conjunction with a radially resolved diffusion model to retrieve translational diffusion coefficients of PEG-4. Comparison of the experimentally derived diffusivities with viscosity estimates for the ternary system reveals a breakdown of the Stokes-Einstein relationship, which has often been invoked to infer diffusivity from viscosity. The evaporation of PEG-4 shows pronounced RH and temperature dependencies and is severely depressed for RH 30 %, corresponding to diffusivities < 10 −14 cm 2 s −1 at temperatures < 15 • C. The temperature dependence is strong, suggesting a diffusion activation energy of about 300 kJ mol −1 . We conclude that atmospheric volatile organic compounds can be subject to severe diffusion limitations in viscous organic aerosol particles. This may enable an important long-range transport mechanism for organic material, including pollutant molecules such as polycyclic aromatic hydrocarbons (PAHs).

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Section: Introductionmentioning

confidence: 99%

Diffusivity measurements of volatile organics in levitated viscous aerosol particles

et al. 2017

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“…Atmospheric aerosols play an important role in Earth's climate system and are linked to adverse health effects (Pope et al 2009;Donahue et al 2012;IPCC 2013;Tsigaridis et al 2014). Organic carbon-based aerosol particles are a major component of ambient aerosol and can make up between 30% and 70% of the total fine aerosol mass (Murphy et al 2006;Zhang et al 2007;Hallquist et al 2009;Emanuelsson et al 2013).…”

Section: Introductionmentioning

confidence: 99%

Advanced aerosol optical tweezers chamber design to facilitate phase-separation and equilibration timescale experiments on complex droplets

Gorkowski

Beydoun

Aboff

et al. 2016

Aerosol Science and Technology

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The phase-separation of mixed aerosol particles and the resulting morphology plays an important role in determining the interactions of liquid aerosols with their gas-phase environment. We present the application of a new aerosol optical tweezers chamber for delivering a uniformly mixed aerosol flow to the trapped droplet's position for performing experiments that determine the phaseseparation and resulting properties of complex mixed droplets. This facilitates stable trapping when adding additional phases through aerosol coagulation, and reproducible measurements of the droplet's equilibration timescale. We demonstrate the trapping of pure organic carbon droplets, which allows us to study the morphology of droplets containing pure hydrocarbon phases to which a second phase is added by coagulation. A series of experiments using simple compounds are presented to establish our ability to use the cavity enhanced Raman spectra to distinguish between homogeneous single-phase, and phase-separated core-shell or partially engulfed morphologies. The core-shell morphology is distinguished by the pattern of the whispering gallery modes (WGMs) in the Raman spectra where the WGMs are influenced by refraction through both phases. A coreshell optimization algorithm was developed to provide a more accurate and detailed analysis of the WGMs than is possible using the homogeneous Mie scattering solution. The unique analytical capabilities of the aerosol optical tweezers provide a new approach for advancing our understanding of the chemical and physical evolution of complex atmospheric particulate matter, and the important environmental impacts of aerosols on atmospheric chemistry, air quality, human health, and climate change. EDITORThomas Kirchstetter

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“…However, our knowledge on organic aerosol (OA) formation, sources, and atmospheric processing is still very incomplete, especially for secondary organic aerosol (SOA) formed from chemical reactions of gas-phase species (e.g., Donahue et al, 2014;Hallquist et al, 2009;Kroll and Seinfeld, 2008;Robinson et al, 2007;Volkamer et al, 2006). Recent progress has been made in identifying primary organic aerosol (POA) sources (e.g., Elbert et al, 2007;Zhang et al, 2005), but significant gaps still remain in our understanding on the atmospheric evolution of POA after emission (de Gouw and Jimenez, 2009).…”

Section: Introductionmentioning

confidence: 99%

Long-term real-time chemical characterization of submicron aerosols at Montsec (southern Pyrenees, 1570 m a.s.l.)

et al. 2015

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Abstract. Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride and black carbon (BC)) and organic submicron aerosols (particles with an aerodynamic diameter of less than 1 µm) from a continental background site (Montsec, MSC, 1570 m a.s.l.) in the western Mediterranean Basin (WMB) were conducted for 10 months (July 2011-April 2012). An aerosol chemical speciation monitor (ACSM) was co-located with other online and offline PM 1 measurements. Analyses of the hourly, diurnal, and seasonal variations are presented here, for the first time, for this region.Seasonal trends in PM 1 components are attributed to variations in evolution of the planetary boundary layer (PBL) height, air mass origin, and meteorological conditions. In summer, the higher temperature and solar radiation increases convection, enhancing the growth of the PBL and the transport of anthropogenic pollutants towards high altitude sites. Furthermore, the regional recirculation of air masses over the WMB creates a continuous increase in the background concentrations of PM 1 components and causes the formation of reservoir layers at relatively high altitudes. The combination of all these atmospheric processes results in a high variability of PM 1 components, with poorly defined daily patterns, except for the organic aerosols (OA). OA was mostly composed (up to 90 %) of oxygenated organic aerosol (OOA), split in two types: semivolatile (SV-OOA) and low-volatility (LV-OOA), the rest being hydrocarbon-like OA (HOA). The marked diurnal cycles of OA components regardless of the air mass origin indicates that they are not only associated with anthropogenic and long-range-transported secondary OA (SOA) but also with recently produced biogenic SOA.Very different conditions drive the aerosol phenomenology in winter at MSC. The thermal inversions and the lower vertical development of the PBL leave MSC in the free troposphere most of the day, being affected by PBL air masses only after midday, when the mountain breezes transport emissions from the adjacent valleys and plains to the top of the mountain. This results in clear diurnal patterns of both organic and inorganic concentrations. OA was also mainly composed (71 %) of OOA, with contributions from HOA (5 %) and biomass burning OA (BBOA; 24 %). Moreover, in winter sporadic long-range transport from mainland Europe is observed.The results obtained in the present study highlight the importance of SOA formation processes at a remote site such as MSC, especially in summer. Additional research is needed to characterize the sources and processes of SOA formation at remote sites.

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Volatility and Aging of Atmospheric Organic Aerosol

Cited by 96 publications

References 194 publications

Diffusivity measurements of volatile organics in levitated viscous aerosol particles

Diffusivity measurements of volatile organics in levitated viscous aerosol particles

Advanced aerosol optical tweezers chamber design to facilitate phase-separation and equilibration timescale experiments on complex droplets

Long-term real-time chemical characterization of submicron aerosols at Montsec (southern Pyrenees, 1570 m a.s.l.)

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