Particles composed of secondary organic material (SOM) are abundant in the lower troposphere. The viscosity of these particles is a fundamental property that is presently poorly quantified yet required for accurate modeling of their formation, growth, evaporation, and environmental impacts. Using two unique techniques, namely a "bead-mobility" technique and a "poke-flow" technique, in conjunction with simulations of fluid flow, the viscosity of the water-soluble component of SOM produced by α-pinene ozonolysis is quantified for 20-to 50-μm particles at 293-295 K. The viscosity is comparable to that of honey at 90% relative humidity (RH), similar to that of peanut butter at 70% RH, and at least as viscous as bitumen at ≤30% RH, implying that the studied SOM ranges from liquid to semisolid or solid across the range of atmospheric RH. These data combined with simple calculations or previous modeling studies are used to show the following: (i) the growth of SOM by the exchange of organic molecules between gas and particle may be confined to the surface region of the particles for RH ≤ 30%; (ii) at ≤30% RH, the particle-mass concentrations of semivolatile and low-volatility organic compounds may be overpredicted by an order of magnitude if instantaneous equilibrium partitioning is assumed in the bulk of SOM particles; and (iii) the diffusivity of semireactive atmospheric oxidants such as ozone may decrease by two to five orders of magnitude for a drop in RH from 90% to 30%. These findings have possible consequences for predictions of air quality, visibility, and climate.aerosol | physical properties | secondary organic aerosol B iological sources (e.g., vegetation) and anthropogenic sources (e.g., transportation) emit copious quantities of volatile organic compounds, such as α-pinene and aromatic hydrocarbons, among others (1, 2). In the atmosphere, a complex series of chemical reactions oxidizes these volatile compounds to form semivolatile organic compounds (SVOCs) that condense to the particle phase (1, 2). This secondary organic material (SOM) constituting the particles is estimated to contribute typically 30-70% to the mass concentration of suspended submicron particles in most regions of the atmosphere (1). These particles can influence climate by scattering and absorbing solar radiation (direct climate effect) and by serving as nuclei for cloud formation (indirect climate effect), among other mechanisms (3). They can also influence air quality and health (4-6).Recently, molecular diffusion within SOM particles has become an area of intense scientific interest. Diffusion rates within particles can influence the mechanism and rates of growth of SOM particles (Fig. 1A) (7,8) and influence reactions of oxidants within the SOM particles (Fig. 1B) (9). As a result, quantitative modeling of the environmental impacts of SOM particles can depend on molecular diffusion within the particles (see, for example, Fig. 1C). Shiraiwa and Seinfeld (10) have shown that predictions of the mass concentration of SOM particles, a ke...

Article:Gaskell, P.H., Jimack, P.K., Sellier, M. et A range of two-and three-dimensional problems is explored featuring the gravitydriven flow of a continuous thin liquid film over a non-porous inclined flat surface containing well-defined topography. These are analysed principally within the framework of the lubrication approximation, where accurate numerical solution of the governing nonlinear equations is achieved using an efficient multigrid solver.Results for flow over one-dimensional steep-sided topographies are shown to be in very good agreement with previously reported data. The accuracy of the lubrication approximation in the context of such topographies is assessed and quantified by comparison with finite element solutions of the full Navier-Stokes equations, and results support the consensus that lubrication theory provides an accurate description of these flows even when its inherent assumptions are not strictly satisfied. The NavierStokes solutions also illustrate the effect of inertia on the capillary ridge/trough and the two-dimensional flow structures caused by steep topography.Solutions obtained for flow over localized topography are shown to be in excellent agreement with the recent experimental results of Decré & Baret (2003) for the motion of thin water films over finite trenches. The spread of the 'bow wave', as measured by the positions of spanwise local extrema in free-surface height, is shown to be well-represented both upstream and downstream of the topography by an inverse hyperbolic cosine function.An explanation, in terms of local flow rate, is given for the presence of the 'downstream surge' following square trenches, and its evolution as trench aspect ratio is increased is discussed. Unlike the upstream capillary ridge, this feature cannot be completely suppressed by increasing the normal component of gravity. The linearity of free-surface response to topographies is explored by superposition of the free surfaces corresponding to two 'equal-but-opposite' topographies. Results confirm the findings of Decré & Baret (2003) that, under the conditions considered, the responses behave in a near-linear fashion.

An efficient full approximation storage (FAS) Multigrid algorithm is used to solve a range of droplet spreading flows modelled as a coupled set of non‐linear lubrication equations. The algorithm is fully implicit and has embedded within it an adaptive time‐stepping scheme that enables the same to be optimized in a controlled manner subject to a specific error tolerance. The method is first validated against a range of analytical and existing numerical predictions commensurate with droplet spreading and then used to simulate a series of new, three‐dimensional flows consisting of droplet motion on substrates containing topographic and wetting heterogeneities. The latter are of particular interest and reveal how droplets can be made to spread preferentially on substrates owing to an interplay between different topographic and surface wetting characteristics. Copyright © 2004 John Wiley & Sons, Ltd.

Abstract. Viscosity in particles consisting of secondary organic material (SOM) has recently become an area of research focus, since information on viscosity is needed to predict the environmental impacts of SOM particles. Recently Renbaum-Wolff et al. (2013a) developed a poke-flow technique that was combined with simulations of fluid flow to constrain the viscosities of SOM samples of 1-5 mg mass, roughly the maximum that may be collected from environmental chambers or flow tubes on a reasonable timescale. The current manuscript expands on the initial validation experiments carried out by Renbaum-Wolff et al. First, the poke-flow technique combined with simulations of fluid flow was used to determine the viscosity of sucrose-water particles over a relatively wide range of relative humidities (RHs). The lower and upper limits of viscosity at 59 % RH were 1.0 × 10 1 and 1.6 × 10 4 Pa s, whilst at 37 % RH the corresponding values were 7.2 × 10 4 and 4.7 × 10 6 Pa s, respectively. The results are in good agreement with recent measurements by Quintas et al. (2006) and Power et al. (2013). Second, the approach was used to determine the viscosity of two polybutene standards. The simulated lower and upper limits of viscosity for standard #1 was 2.0 × 10 2 and 1.2 × 10 4 Pa s, whilst for standard #2 the corresponding values were 3.1 × 10 2 and 2.4 × 10 4 Pa s. These values are in good agreement with values reported by the manufacturer. The results for both the sucrose-water particles and the polybutene standards show that the poke-flow technique combined with simulations of fluid flow is capable of providing both lower and upper limits of viscosity that are consistent with literature or measured values when the viscosity of the particles are in the range of ≈ 5 × 10 2 to ≈ 3 × 10 6 Pa s.

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