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The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI)xM(+) (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

Improved methods are needed to study sorption of vapor molecules by particles in the gas phase (heterogeneous uptake), which is an important process in both natural and engineered environments. Here, a new measurement system, composed of a differential mobility analyzer (DMA) and drift tube ion mobility spectrometer (DTIMS) in series, is used to examine the heterogeneous uptake of water vapor by 2.85-7.6 nm particles composed of lithium and sodium iodide. The extent of heterogeneous uptake is determined by controlling the relative humidity of the drift region in the DTIMS in the 0-30% range (in air at atmospheric pressure and room temperature), and is quantified via the dimensionless growth factor (GF), i.e. the ratio of the mobility diameter of particles at a prescribed relative humidity relative to their mobility diameter under dry conditions. The precision in GF estimation of the DMA-DTIMS system is shown to be below 0.2%. An analytical equation to calculate the growth factor, based upon predictions of the equilibrium constants for the successive uptake of vapor molecules by particles, is also presented. While the equation is sufficiently general to enable comparison between measured GFs and predictions from any theoretical expression for equilibrium constants, we specifically compare measurements to GF predictions based on the classical Kelvin-Thomson-Raoult (KTR) model for the vapor pressure of a small particle, with consideration of the influence of the ion-dipole potential on water vapor-nanoparticle collisions. It is shown that KTR calculations drastically underpredict the extent of heterogeneous uptake for the examined nanoparticles.

TSI Inc. (Shoreview, MN) has introduced three new waterbased condensation particle counters (WCPCS) that were designed to detect airborne particles larger than 2.5 nm (model 3786), 5 nm (model 3785), and either 10 or 20 nm (model 3782). These WCPCs are well suited for real-time, environmental monitoring of number concentration of airborne ultrafine particles. Their unique design incorporates the use of water as the working fluid instead of alcohol. Water is odor free, readily available, and eliminates the problem of water condensation and absorption into alcohol working fluids during operation in humid environments. In this study, the performance of three TSI WCPCs was characterized for several aerosol compositions, including sucrose, salt (NaCl), dioctyl sebacate (DOS), dioctyl phthalate (DOP), emery oil (poly-alphaolefin), silver, impurity residue particles, and ambient aerosol particles. All particles were size selected using a nano differential mobility analyzer (nano-DMA; model 3085, TSI Inc.) to create monodisperse challenge aerosols. The challenge aerosol was mixed uniformly with clean makeup flow and split into a WCPC and a reference instrument to determine the counting efficiency of the WCPC. For the model 3785 WCPC, the D 50 (i.e., the particle diameter with 50% counting efficiency) was determined to be 3

We apply liquid nebulization (LN) in series with ion mobility spectrometry (IMS, using a differential mobility analyzer coupled to a condensation particle counter) to measure the size distribution functions (the number concentration per unit log diameter) of gold nanospheres in the 5-30 nm range, 70 nm × 11.7 nm gold nanorods, and albumin proteins originally in aqueous suspensions. In prior studies, IMS measurements have only been carried out for colloidal nanoparticles in this size range using electrosprays for aerosolization, as traditional nebulizers produce supermicrometer droplets which leave residue particles from non-volatile species. Residue particles mask the size distribution of the particles of interest. Uniquely, the LN employed in this study uses both online dilution (with dilution factors of up to 10(4)) with ultra-high purity water and a ball-impactor to remove droplets larger than 500 nm in diameter. This combination enables hydrosol-to-aerosol conversion preserving the size and morphology of particles, and also enables higher non-volatile residue tolerance than electrospray based aerosolization. Through LN-IMS measurements we show that the size distribution functions of narrowly distributed but similarly sized particles can be distinguished from one another, which is not possible with Nanoparticle Tracking Analysis in the sub-30 nm size range. Through comparison to electron microscopy measurements, we find that the size distribution functions inferred via LN-IMS measurements correspond to the particle sizes coated by surfactants, i.e. as they persist in colloidal suspensions. Finally, we show that the gas phase particle concentrations inferred from IMS size distribution functions are functions of only of the liquid phase particle concentration, and are independent of particle size, shape, and chemical composition. Therefore LN-IMS enables characterization of the size, yield, and polydispersity of sub-30 nm particles.

The ability of the Model 3320 aerodynamic particle sizer (APS) to make accurate mass-weighted size distribution measurements was investigated. Signi cant errors were observed in APS size distribution measurements with measured mass median aerodynamic diameters (MMADs) as much as 17 times higher than from cascade impactor measurements. Analysis of APS correlated timeof-ight and light scattering data indicated that the MMAD distortions were due to a few anomalous large particle measurements (» 0.1% of the total measurements) with surprisingly low scattered light. Computational uid dynamics modeling indicated that these anomalous measurements were due to particles that deviated from the intended aerosol pathway and recirculated through the APS measurement volume at low velocities leading to erroneous large particle measurements. A technique for removing erroneous measurements based on correlated aerodynamic diameter and light scattering values is presented. When this technique was used, APS and cascade impactor size distribution measurements agreed well.