Lindsay Renbaum-Wolff

Viscosity of α-pinene secondary organic material and implications for particle growth and reactivity

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.

Images reveal that atmospheric particles can undergo liquid–liquid phase separations

A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquid–liquid phase separation. If liquid–liquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquid–liquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquid–liquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquid–liquid phase separation can result in increased concentrations of gas-phase NO3 and N2O5 due to decreased particle uptake of N2O5.

A Calibration Technique for Improving Refractive Index Retrieval from Aerosol Cavity Ring-Down Spectroscopy

Cavity ring-down spectroscopy (CRDS) is a technique that is commonly used to measure the extinction of light by aerosol particles in situ. This extinction, when normalized to particle concentration, yields the extinction cross section, a measure of a single particles ability to scatter and absorb light. The complex index of refraction can then be retrieved by comparison of the extinction cross sections at several particle diameters with those predicted by Mie theory. This approach requires accurate determination of particle diameter and concentration as well as the length of the extinction region in the cavity, but it is often difficult to quantify the systematic errors in the measurements of these quantities. Here, we introduce a calibration technique using particles of a reference compound to account for these systematic errors. The two calibration parameters are: Cf , which scales the measured extinction cross sections, and Δd, which shifts the particle diameters. It is found that Cf correlates strongly with the condensation particle counter (CPC) used to measure particle concentration and that Δd is associated with the differential mobility analyzer (DMA) used to select particle diameters. Calibration is shown to reduce errors of subsequently-measured extinction cross sections of a test aerosol from 11% to with a concomitant improvement in the accuracy of the retrieved complex index of refraction and corresponding atmospheric radiative forcing estimates. Copyright 2013 American Association for Aerosol Research

Estimating the viscosity of a highly viscous liquid droplet through the relaxation time of a dry spot

We discuss in this paper a technique which enables the estimation of the viscosity of microscopic droplets, with application to particles suspended in the atmosphere. The principle of this technique is to deposit a droplet of material approximately 30–100 μm in diameter on a substrate and poke it with a sharp needle hence generating a hole. The amount of sample needed to perform such measurement allows the viscosity of small sample volumes (less than a microliter), such as those generated from atmospheric sampling, to be determined. We show here that the time required for the droplet to relax to its equilibrium shape can be related to the viscosity. We hereby present two mathematical models based on the lubrication approximation which are able to capture the droplet relaxation dynamics. One model is fully transient and resolves the dynamics of the wetting front using a disjoining pressure approach. The other is quasistatic and requires a relationship between the contact line velocity and the contact angle...

Laboratory evaluation of species-dependent relative ionization efficiencies in the Aerodyne Aerosol Mass Spectrometer

ABSTRACT Mass concentrations calculated from Aerodynes aerosol mass spectrometers depend on particle collection efficiency (CE) and relative ionization efficiency (RIE, relative to the primary calibrant ammonium nitrate). We present new laboratory RIE measurements for a wide range of organic aerosol species (RIEOA). An improved laboratory RIE calibration protocol with size and mass selection of calibrant particles and a light scattering-based detection of CE is used. Simpler calibrations of alcohol RIEs using binary mixtures with NH4NO3 are demonstrated. Models that account for only thermal velocity and electron ionization of vaporized molecules do not reproduce RIEOA measurements, confirming that other processes are significant. The relationship between RIEOA and average carbon oxidation state (), a metric used to describe atmospheric OA, is investigated. An average RIEOA of 1.6 ± 0.5 (2σ) is found for −1.0 < < 0.5, a range consistent with most ambient OA except hydrocarbon-like organic aerosol (HOA) and cooking organic aerosol (COA). RIEOA from 2 to 7 are found for below and above this range. The RIEOA typically used for ambient OA (1.4 ± 0.3) is within the laboratory RIEOA measurement uncertainty of oxidized organic species, but is a factor of 2 to 5 lower than that of reduced species. Such biases in OA mass concentrations have not been observed in published field analyses. Chemically reduced ambient OA may have composition, phase states, or compensating CE effects that are not mimicked well in the laboratory. This work highlights the need for further ambient OA studies to better constrain the composition dependence of ambient RIEOA, and the need to always calibrate with the OA under study for laboratory experiments. Copyright