Derek R. Oberreit

A Laminar-Flow, Water-Based Condensation Particle Counter (WCPC)

A new water-based condensation particle counter (WCPC) is presented. The WCPC is a thermally diffusive, laminar flow instrument. Condensational enlargement is achieved through the introduction of a saturated airflow into a “growth tube” with wetted walls held at a temperature higher than that of the entering flow. An unsheathed, 1 L/min instrument utilizing this principle has been evaluated with various aerosols. The particle size detected with an efficiency of 50% is at or below 4.8 nm for particles sampled from vehicular emissions or ambient air, and for various laboratory-generated inorganic salts. The cut point is higher for the organic materials tested, ranging from 8 nm to 30 nm depending on the compound and purity level. An empirically determined dead-time correction factor is applied to the coincidence correction, which allows extension of the single-count mode to higher concentrations. The counting efficiencies for 80 nm oil and salt aerosols are equal, and above 97% for concentrations approaching 10 5 cm −3 . When subject to a step-fucntion change in input concentration the time required to attain 90% of the final value, including a 0.5 s lag, is 1.3 s. The corresponding exponential time constant is 0.35 s. The WCPC evaluated here is marketed as the TSI Model 3785.

An evaluation of mass-weighted size distribution measurements with the Model 3320 aerodynamic particle sizer

The ability of the Model 3320 aerodynamic particle sizer (APS) to make accurate mass-weighted size distribution measurements was investigated. Significant 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 time-of-flight 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 fluid 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.

Water-based condensation particle counters for environmental monitoring of ultrafine particles.

Abstract TSI Inc. (Shoreview, MN) has introduced three new water-based 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-alpha-olefin), 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 D50 (i.e., the particle diameter with 50% counting efficiency) was determined to be 3.1 nm for salt particles, 4.7 nm for sucrose and ambient particles, 5.6 nm for silver particles, and >50 nm for ultrapure oil particles. The sensitivity to oil droplets increased dramatically (D50 < 10 nm) when the oil was slightly contaminated. The D50 of model 3786 ultra-fine water-based CPC (UWCPC) was 2.4 nm for impurity residue particles. The D50 of the model 3782 WCPC was 10.8 (with a nominal setting of 10 nm) or 19.8 nm (with a nominal setting of 20 nm) for sucrose particles. All three WCPCs have response times of less than 2 or 3 sec and are therefore able to detect fast-changing events.

An Ultrafine, Water-Based Condensation Particle Counter and its Evaluation under Field Conditions

An ultrafine, water-based condensation particle counter (U-WCPC, TSI Model 3786) has been compared to a butanol-based ultrafine counter (U-BCPC, TSI Model 3025) for measurement of atmospheric and freeway-tunnel aerosols. The U-WCPC utilizes a warm, wet-walled growth tube to activate and grow particles through water condensation in a laminar-flow. It has an aerosol sampling rate of 0.3 L/min, and a nominal detection limit near 3 nm. Several field comparisons were made to the butanol-based instrument with the same nominal detection limit. For measurements of size-selected aerosols with diameters of 5 nm and larger the two instruments generally agreed, with a mean response within 5%. At 3 nm particle size differences were observed, and these differences varied with the data set. Measurements of ambient aerosol in Boulder, Colorado showed higher counting efficiency at 3 nm with the U-BCPC, while in a California freeway tunnel the opposite trend was observed, with higher counting efficiencies at 3 nm observed by the U-WCPC. For direct measurement of atmospheric aerosols, the two types of instruments yielded equivalent concentrations, independent of particle number concentration.

Analysis of heterogeneous uptake by nanoparticles via differential mobility analysis–drift tube ion mobility spectrometry

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.

Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

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.

Mobility Analysis of 2 nm to 11 nm Aerosol Particles with an Aspirating Drift Tube Ion Mobility Spectrometer

We describe the performance of a drift tube-ion mobility spectrometry (DT-IMS) instrument for the measurement of aerosol particles. In DT-IMS, the electrical mobility of a measured particle is inferred directly from the time required for the particle to traverse a drift region, with motion driven by an electrostatic field. Electrical mobility distributions are hence linked to arrival time distributions (ATDs) for particles reaching a detector downstream of the drift region. The developed instrument addresses two obstacles that have limited DT-IMS use for aerosol measurement previously: (1) conventional drift tubes cannot efficiently sample charged particles at ground potential and (2) the sensitivities of commonly used Faraday plate detectors are too low for most aerosols. Obstacle (1) is circumvented by creating a “sample volume” of aerosol for measurement, defined by the streamlines of fluid flow. Obstacle (2) is bypassed by interfacing the end of the drift region with a condensation particle counter. The DT-IMS prototype shows high linearity for arrival time versus inverse electrical mobility (R 2 > 0.99) over the size range tested (2.2–11.1 nm), and measurements compare well with both analytical and numerical models of device performance. A dimensionless calibration curve linking drift time to inverse electrical mobility is developed. In less than 5 s, it is possible to measure 11.1 nm particles, while 2.2 nm particles are analyzable on a subsecond scale. The transmission efficiency is found to be dependent upon electrostatic deposition for short drift times and upon advective losses for long drift times. Copyright 2014 American Association for Aerosol Research

Collision-Based Ionization: Bridging the Gap between Chemical Ionization and Aerosol Particle Diffusion Charging

In diffusion charging theory, it is assumed that each ion–particle collision leads to the transfer of charge from ion to particle, and that charge transfer will not occur upon collision between a vapor molecule and a charged particle. However, in chemical ionization, charge transfer can occur in two directions—from charge-donating ion to vapor molecule and back from charged vapor molecule to the original charge-donating species. Both aerosol diffusion charging and chemical ionization are collision-based charge transfer processes, and for particles only slightly larger than vapor molecules (aerosol clusters), the line between diffusion charging and chemical ionization becomes blurred. We examined the charge transfer from aerosol clusters (positively charged amino acid clusters) in the ∼1.0 nm size range to neutral vapor molecules (trimethylamine) at atmospheric pressure by using a combined experimental and theoretical approach. It was found that for singly charged amino acid cluster ions composed of 1, 2, and 3 amino acid molecules, the rate of charge transfer to trimethylamine vapor molecules was clearly observable, particularly for clusters composed of 1 and 2 molecules. The charge transfer rate for singly charged clusters with 4 or more amino acid molecules was consistently close to 0, indicating that the rate of charge transfer from clusters to vapor molecules is size dependent. The charge transfer rates also varied with clusters chemical composition. Overall, this study demonstrates that small aerosol clusters (∼0.5 nm) can lose charge through collisions with vapor molecules, which is typically not considered in diffusion charging theories.

Liquid Nebulization–Ion Mobility Spectrometry Based Quantification of Nanoparticle–Protein Conjugate Formation

Despite the importance of examining the formation of nanoparticle-protein conjugates, there is a dearth of routine techniques for nanoparticle-protein conjugate characterization. The most prominent change to a nanoparticle population upon conjugate formation is a shift in the nanoparticle size distribution function. However, commonly employed dynamic light scattering based approaches for size distribution characterization are ineffective for nonmonodisperse samples, and further they are relatively insensitive to size shifts of only several nanometers, which are common during conjugate formation. Conversely, gas phase ion mobility spectrometry (IMS) techniques can be used to reliably examine polydisperse samples, and are sensitive to ∼1 nm size distribution function shifts; the challenge with IMS is to convert nanoparticle-protein conjugates to aerosol particles without bringing about nonspecific aggregation or conjugate formation. Except in limited circumstances, electrospray based aerosolization has proven difficult to apply for this purpose. Here we show that via liquid nebulization (LN) with online, high-flow-rate dilution (with dilution factors up to 10 000) it is possible to aerosolize nanoparticle-protein conjugates, enabling IMS measurements of their conjugate size distribution functions. We specifically employ the LN-IMS system to examine bovine serum albumin binding to gold nanoparticles. Inferred maximum protein surface coverages (∼0.025 nm(-2)) from measurements are shown to be in excellent agreement with reported values for gold from quartz crystal microbalance measurements. It is also shown that LN-IMS measurements can be used to detect size distribution function shifts on the order of 1 nm, even in circumstances where the size distribution function itself has a standard deviation of ∼5 nm. In total, the reported measurements suggest that LN-IMS is a potentially simple and robust technique for nanoparticle-protein conjugate characterization.

Ion-Mobility-Based Quantification of Surface-Coating-Dependent Binding of Serum Albumin to Superparamagnetic Iron Oxide Nanoparticles

Protein binding and protein-induced nanoparticle aggregation are known to occur for a variety of nanomaterials, with the extent of binding and aggregation highly dependent on nanoparticle surface properties. However, often lacking are techniques that enable quantification of the extent of protein binding and aggregation, particularly for nanoparticles with polydisperse size distributions. In this study, we adapt ion mobility spectrometry (IMS) to examine the binding of bovine serum albumin to commercially available anionic-surfactant-coated superparamagnetic iron oxide nanoparticles (SPIONs), which are initially ∼21 nm in mean mobility diameter and have a polydisperse size distribution function (geometric standard deviation near 1.4). IMS, carried out with a hydrosol-to-aerosol converting nebulizer, a differential mobility analyzer, and a condensation particle counter, enables measurements of SPION size distribution functions for varying BSA/SPION number concentration ratios. IMS measurements suggest that initially (at BSA concentrations below 50 nM) BSA binds reversibly to SPION surfaces with a binding site density in the 0.05-0.08 nm(-2) range. However, at higher BSA concentrations, BSA induces SPION-SPION aggregation, evidenced by larger shifts in SPION size distribution functions (mean diameters beyond 40 nm for BSA concentrations near 100 nM) and geometric standard deviations (near 1.3) consistent with self-preserving aggregation theories. The onset of BSA aggregation is correlated with a modest but statistically significant decrease in the specific absorption rate (SAR) of SPIONs placed within an alternating magnetic field. The coating of SPIONs with mesoporous silica (MS-SPIONs) as well as PEGylation (MS-SPIONs-PEG) is found to completely mitigate BSA binding and BSA-induced aggregation; IMS-inferred size distribution functions are insensitive to BSA concentration for MS-SPIONs and MS-SPIONs-PEG. The SARs of MS-SPIONs are additionally insensitive to BSA concentration, confirming the SAR decrease is linked to BSA-induced aggregation.