Coincidence in Time-of-Flight Aerosol Spectrometers: Phantom Particle Creation

When using time-of-flight aerosol spectrometers, particle size measurement is based upon a particle's transit time between two laser beams. The particle's transit time is assumed to be the time difference between the two pulses of light that are produced as the particle passes through the two laser beams. Particle coincidence, which occurs when a second particle crosses the first laser beam before the first particle crosses the second laser beam, has a complex effect upon the measured size distribution. As a result of coincidence, time-of-flight aerosol spectrometers can replace real particles of one size with spurious, or phantom, particles of a different size in the measured distribution. When partial detection of a particle occurs, i.e., only one pulse from a particle is detected, another particle producing a pulse that occurs while the timer is open can cause the recording of a randomly sized phantom particle. The creation of these phantom particles, which we termed “open-timer” phantom particles, has been investigated theoretically and experimentally in a commercially available time-of-flight aerosol spectrometer. The number of these open-timer phantom particles was found to increase with particle size and aerosol concentration. In addition, the instrument's detection logic affects the number and size of the phantom particles. These are most apparent in the tails and minima of the measured distribution. In order to minimize phantom particle creation, the concentration of partially detected particles must be minimized. Strategies to reduce phantom particle concentration involve reducing the concentration of small particles near the optical detection threshold of the spectrometer.     

A New Laser Induced Incandescence–Mass Spectrometric Analyzer (LII-MS) for Online Measurement of Aerosol Composition Classified by Black Carbon Mixing State

We developed a laser induced incandescence–mass spectrometric analyzer (LII-MS) for online measurements quantifying the aerosol chemical compositions with respect to the mixing state of black carbon (BC). The LII-MS is developed as a tandem series comprising an LII chamber to detect and vaporize BC-containing particles and a particle trap laser desorption mass spectrometer (PT-LDMS: Takegawa et al. 2012). The PT-LDMS collects aerosol particles transferred from the LII chamber and quantifies the chemical compositions. A newly designed collection probe, coupled with the sheath-air inlet nozzle of the LII chamber, enables a high throughput of aerosol particles without significant dilution. Total aerosol particles can be analyzed in the PT-LDMS by turning off the laser (MS mode), and the aerosol particles externally mixed with BC can be analyzed by turning on the laser (LII-MS mode). The difference in the PT-LDMS signals between the MS and LII-MS modes yields the chemical composition of materials internally mixed with BC. Performance of the developed instrument was evaluated in the laboratory by generating BC particles internally-mixed with oleic acid (OL) and BC particles externally mixed with ammonium sulfate particles. Preliminary results from ambient measurements are also presented and discussed.

Copyright 2014 American Association for Aerosol Research     

Size Resolution of Laser Optical Particle Counters

The size-resolving capabilities of laser optical particle counters have been explored. The ideal size resolution displays a singular behavior (i.e., the leading edge of the pulse height spectrum observed when calibrating with strict monodisperse aerosol increases, whereas the trailing edge falls off infinitely). When a real test aerosol is used the singularity is suppressed; as a consequence, it has become common practice to take the observed regular pulse height spectrum as “the” resolution.

The tendency to judge the alignment of laser optical particle counters from the symmetry of the observed pulse height spectrum results in definite alignment errors, with a serious deterioration in functioning. The ambient Junge size distribution will not be distorted when sizing it by means of a laser optical particle counter. Essentially, the particle size-dependent number concentration will be underestimated up to some 15% for large particles.

When interpreting measured size distributions using a commonly assumed Gaussian resolution, differences of up to some 25% could result, particularly in the large size regime.     

Calibration of a particle mass spectrometer using polydispersed aerosol particles

Routine calibrations of online aerosol chemical composition analyzers are important for assessing data quality during field measurements. The combination of a differential mobility analyzer (DMA) and condensation particle counter (CPC) is a reliable, conventional method for calibrations. However, some logistical issues arise, including the use of radioactive material, quality control, and deployment costs. Herein, we propose a new, simple calibration method for a particle mass spectrometer using polydispersed aerosol particles combined with an optical particle sizer. We used a laser-induced incandescence–mass spectrometric analyzer (LII-MS) to test the new method. Polydispersed aerosol particles of selected chemical compounds (ammonium sulfate and potassium nitrate) were generated by an aerosol atomizer. The LII section was used as an optical particle sizer for measuring number/volume size distributions of polydispersed aerosol particles. The calibration of the MS section was performed based on the mass concentrations of polydispersed aerosol particles estimated from the integration of the volume size distributions. The accuracy of the particle sizing for each compound is a key issue and was evaluated by measuring optical pulse height distributions for monodispersed ammonium sulfate and potassium nitrate particles as well as polystyrene latex particles. A comparison of the proposed method with the conventional DMA-CPC method and its potential uncertainties are discussed.

Copyright © 2018 American Association for Aerosol Research     

Investigation of the size of the incandescent incipient soot particles in premixed sooting and nucleation flames of n-butane using LII,HIM, and 1 nm-SMPS

Laser-induced incandescence (LII) measurements were conducted to explore the ability of LII to detect small soot particles of less than 10 nm in two sooting flat premixed flames of n-butane: a so-called nucleation flame obtained at a threshold equivalence ratio Φ = 1.75, in which the incipient soot particles undergo only minor soot surface growth along the flame, and a more sooting flame at Φ = 1.95. Size measurements were obtained by modeling the time-resolved LII signals detected using 1064 nm laser excitation. Spectrally-resolved LII signals collected in the nucleation flame display a similar blackbody-like behavior as mature soot. Soot particle temperature was determined from spectrally-resolved detection. LII modeling was conducted using parameters either relevant to those of mature soot or derived from fitting the modeled results to the experimental LII data. Particle size measurements were also carried out using (1) ex situ analysis by helium-ion microscopy (HIM) of particles sampled thermophoretically and (2) online size distribution analysis of microprobe-sampled particles using a 1 nm-SMPS. The size distributions of the incipient soot particles, found in the nucleation flame and in the early soot region of the Φ = 1.95 flame, derived from time-resolved LII signals are in good agreement with HIM and 1 nm-SMPS measurements and are in the range of 2–4 nm. The thermal and optical properties of incipient soot were found to be not radically different from those of mature soot commonly used in LII modeling. This explains the ability of incipient soot particles to produce continuous thermal emissions in the visible spectrum. This study demonstrates that LII is a promising in situ optical particle sizing technique that is capable of detecting incipient soot as small as about 2.5 nm and potentially 2 nm and resolving small changes in soot sizes below 10 nm.

© 2017 American Association for Aerosol Research     

COUNTING EFFICIENCY OF THE API AEROSIZER

The Aerosizer (Amherst Process Instruments, Inc. Hadley MA) is a time-of-flight instrument frequently used to measure the size distribution of an aerosol. However, if the Aerosizer’s counting efficiency, defined as the number of particles counted divided by the total number entering the instrument, is not 100% or varies with particle size, the resulting size distribution will be inaccurate.Experiments were conducted to determine the effect of particle diameter, particle concentration, photomultiplier tube (PMT) voltage, and model type on the Aerosizer’s counting efficiency. To calculate counting efficiency, the number of particles between 0.3 and 10 μm recorded by the Aerosizer was divided by the number of particles of the same size collected on each stage of a cascade impactor.Particle diameter, aerosol concentration, Aerosizer model, PMT voltage, and the diameter interaction terms influenced counting efficiency. Counting efficiencies were less than 1% for particles smaller than 0.45 μm, and more than 100% for particles larger than 7 μm. Increasing the PMT voltage increased the counting efficiency for the smaller particles, but also created false, larger particles. Counting efficiency decreased as count rate increased for count rates greater than 20,000 particles per second. The Aerosizer LD counted particles more efficiently than the Aerosizer Mach 2 because of improved laser and optics systems. Four regression models that relate counting efficiency to the salient operating parameters were developed, one for each combination of Aerosizer model and photomultiplier tube voltage studied.     

New fast integrated mobility spectrometer for real-time measurement of aerosol size distribution—I: Concept and theory

A new instrument capable of measuring aerosol size distribution with high time and size resolution, and high signal-to-noise ratios is described. The instrument, referred to as Fast Integrated Mobility Spectrometer (FIMS), separates charged particles based on their electrical mobility into different trajectories in a uniform electric field. The particles are then grown into super-micrometer droplets, and their locations on the trajectories are recorded by a fast charge-coupled device (CCD) imaging system. Images captured by the CCD reveal mobility-dependent particle positions and their numbers, which are then used to derive a particle size distribution spectrum. By eliminating the need to scan over a range of voltages, FIMS significantly improves the measurement speed and counting statistics. A theoretical framework has been developed to quantify the measurement range, mobility resolution, and transfer function of FIMS. It is shown that FIMS is capable of measuring aerosol size distributions with high-time and size resolution.     

Sizing Small Sulfuric Acid Particles with an Ultrafine Particle Condensation Nucleus Counter

The sizing capability of an ultrafine particle condensation nucleus counter (which uses butanol as the condensing fluid) equipped with pulse height analysis was evaluated in terms of particle composition for sulfuric acid aerosol and sulfuric acid aerosol to which gas-phase ammonia had been added. The response of the counter depended on composition for a range of particle sizes when the water partial pressure was low. For water partial pressures < 5 Torr and for particles > 4 nm in diameter, the response (pulse heights) of the instrument to particles of a given size was substantially different for sulfuric acid particles and those that were neutralized with ammonia. For water partial pressures > 5 Torr, however, neutralizing the particles with ammonia had little effect on pulse height distributions. For particles smaller than 4 nm diameter the pulse heights were insensitive to exposure to ammonia.     

Detection and Analysis of Aerosol Particles by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was evaluated as a means for quantitative analysis of the size, mass, and composition of individual micron-to submicron-sized aerosol particles over a range of well-characterized experimental conditions. Conditional data analysis was used to identify LIBS spectra that correspond to discrete aerosol particles under low aerosol particle loadings. The size distributions of monodisperse particle source flows were measured using the LIBS technique for calcium- and magnesium-based aerosols. The resulting size distributions were in good agreement with independently measured size distribution data. A lower size detection limit of 175 nm was determined for the calcium- and magnesium-based particles, which corresponds to a detectable mass of approximately 3 femtograms. In addition, the accuracy of the LIBS technique for the interference-free analysis of different particle types was verified using a binary aerosol system of calcium-based and chromium particles.     

Preparation of poly(L-lactic acid) submicron particles in aerosol solvent extraction system using supercritical carbon dioxide

The aerosol solvent extraction system process (ASES), which is one of the supercritical anti solvent processes (SAS), was used to produce poly(L-lactic acid) (PLLA) into the submicron particles. Dichloromethane (DCM, CH₂Cl₂) and carbon dioxide were selected as a solvent and as an antisolvent for PLLA, respectively. The objective of this study was to investigate the effect of the various process parameters such as temperature, pressure, and solution concentration on PLLA particles. With increasing temperature and pressure, particle size was increased. Also, higher PLLA concentration led to larger particle size and broader particle size distribution. A scanning electron microscope (SEM) was used to observe the morphology and size of PLLA particles recrystallized by ASES process. The mean particle size and its distribution of processed particles were measured by using a laser diffraction particle size analyzer (PSA).     

Design and performance test of a multi-channel diffusion charger for real-time measurements of submicron aerosol particles having a unimodal log-normal size distribution

It is important to develop a simple and fast method for measuring the sizes of submicron particles in both laboratories and fields. In our previous studies, Park, An, and Hwang [(2007). Development and performance test of a unipolar diffusion charger for real-time measurements of submicron aerosol particles having a log-normal size distribution. Journal of Aerosol Science, 38, 420–430] and Park, Kim, An, and Hwang [(2007). Real-time measurement of submicron aerosol particles having a log-normal size distribution by simultaneously using unipolar diffusion charger and unipolar field charger. Journal of Aerosol Science, 38, 1240–245], we introduced methodologies that our lab made unipolar charger could lead to detection times of under 5 s in conjunction with an electrometer and a condensation particle counter (CPC), and under 3 s with two electrometers.However, both methodologies require an appropriate assumption of the geometric standard deviation of particle sizes. In this paper, we introduce a methodology for determining the geometric standard deviation of particle sizes as well as the geometric mean diameter and the total number concentration of particles. For this purpose, a diffusion charger that consisted of discharge zone, mixing and charging zone, and three flow channels for obtaining three different residence times and average charges of particles in the channels, was designed and tested. For determining the average particle charge, various methods including theoretical calculations and the tandem differential mobility analyzer (TDMA) method were used. The results obtained from the different methods agreed well with each other. To compare the size distribution with the data that were measured through a scanning mobility particle sizer (SMPS), sodium chloride (NaCl) particles were used. The estimated results by using a data inversion algorithm were less than those measured by SMPS by around 22% for the total number concentration and 10% for both the geometric mean diameter and the geometric standard deviation. Furthermore, the detection time was under 3 s.     

Wavelength and temperature dependences of the absorption and scattering cross sections of soot

We have inferred the wavelength and temperature dependence of the absorption and scattering cross sections of mature soot in an ethylene flame from laser-induced incandescence (LII) and transmittance measurements at 532 and 1064 nm. The LII measurements indicate that the emissivity of soot in a flame deviates from the expected 1/λ dependence. Combining the LII results with transmittance measurements yields single-scattering albedos of 0.058-0.077 at 1064 nm and 0.22-0.29 at 532 nm and values of F(m)/E(m) of 2.2-2.9 at 532 nm and 2.4-3.3 at 1064 nm. These values confirm that scattering must be taken into account when interpreting extinction data at these wavelengths. Our results also indicate increases in the absorption cross section and decreases in the scattering cross section with increasing fluence at low fluences. The increase in absorption cross section is consistent with increases in primary particle size with increasing particle temperature during laser heating. The decrease in scattering cross section could be attributable to an increase in the radius of gyration or a decrease in the fractal dimension of the aggregate with increasing temperature. Alternatively these trends might be the result of changes to the optical properties of the particles with increasing temperature.     

Development of a fast-response, high-resolution electrical mobility spectrometer

A short electrical mobility spectrometer (EMS) for measuring aerosol size distribution has been developed and presented [Intra and Tippayawong, Korean J. Chem. Eng., 26, 1770, 2009]. In this work, further improvement of the short EMS into a fast-response, and high resolution instrument is presented. This was done by (i) improvement in particle charging, (ii) utilization of faster flow rate, and (iii) adoption of higher number of electrode rings. The so-called ??long?? EMS consists of three main parts: a particle charger, a long multi-channel size classifier column, and a multichannel electrometer. Performance of the long EMS was preliminarily tested using polydisperse, carbonaceous aerosol particles generated by a diffusion flame. Preliminary test results showed that the long EMS performed comparatively well, and gave faster response and higher resolution than the short EMS. It was a valuable aerosol instrument available for measuring size distribution of aerosol particles.     

Multiple charging of ultrafine particles in a corona charger

The charge distribution on ultrafine aerosol particles in the size range below 35 nm has been measured using a corona-based unipolar charger, in which ion generation and aerosol charging take place simultaneously in the region around a sharp-point discharge electrode. The mean number of charges per particle predicted by Fuchs’ diffusion charging theory is in relatively good agreement with the experimental results, and this implies that diffusion charging is the predominant mechanism in spite that the electric field in the charging region is very high. Since a steady state is unattainable in unipolar charging, the charge distribution depends on the geometry and operating conditions of each particular charger. When the present device operates under the conditions (nt-product) which yield the maximum charging efficiency, double charge appears on particles with diameter as small as 15 nm. At larger values of nt, 32 nm particles can acquire up to five charges. The critical particle diameter above which multiple charging occurs is about four times smaller than for bipolar radioactive chargers. In order to use corona charging in aerosol particle size measurement by electrical methods, the required mobility data inversion is thus straightforward for particle diameter below about 15 nm, but becomes quite complex for larger sizes.     

THE ON-LINE CHEMICAL ANALYSIS OF SINGLE PARTICLES USING AEROSOL BEAMS AND TIME OF FLIGHT MASS SPECTROMETRY

This paper describes an on-line instrument, capable of measuring the size and chemical composition of single, aerosol particles. Possible applications include monitoring aerosol reactors and studying atmospheric chemistry. The main conclusion is that a working prototype has been built and tested. It uses a three stage vacuum system to generate an aerosol beam with a low divergence angle and a high transmittance. The pressure is reduced sufficiently to allow the application of a time-of-flight mass analyzer. The aerosol beam is probed in the analysis section by the focused beam of a low-power helium-neon laser. Every particle crossing the laser beam scatters light, which is detected by two photomultiplier tubes, mounted at angles of 45 and 90°. The signal is stored when both detectors produce a pulse simultaneously, and this event triggers the chemical analysis cycle. A pulsed Nd: YAG laser vaporizes the particle and generates ions, which are next analyzed by a time-of-flight mass spectrometer. In this way combined information on the size and the composition of the particle is obtained.     

A Novel Optical Instrument for Estimating Size Segregated Aerosol Mass Concentration in Real Time

A novel optical instrument has been developed that estimates size segregated aerosol mass concentration (i.e., PM ₁₀ , PM ₄ , PM _2.5 , and PM ₁ ) over a wide concentration range (0.001–150 mg/m ³ ) in real time. This instrument combines photometric measurement of the particle cloud and optical sizing of single particles in a single optical system. The photometric signal is calibrated to approximate the PM _2.5 fraction of the particulate mass, the size range over which the photometric signal is most sensitive. The electrical pulse heights generated by light scattering from particles larger than 1 micron are calibrated to approximate the aerodynamic diameter of an aerosol of given physical properties, from which the aerosol mass distribution can be inferred. By combining the photometric and optical pulse measurements, this instrument can estimate aerosol mass concentrations higher than typical single particle counting instruments while providing size information and more accurate mass concentration information than traditional photometers. Experiments have shown that this instrument can be calibrated to measure aerosols with very different properties and yet achieve reasonable accuracy.     

Simulation of Aerosol Dynamics: A Comparative Review of Algorithms Used in Air Quality Models

A comparative review of algorithms currently used in air quality models to simulate aerosol dynamics is presented. This review addresses coagula tion, condensational growth, nucleation, and gas particle mass transfer. Two major approaches are used in air quality models to represent the particle size distribution: (1) the sectional approach in which the size distribution is discretized into sections and particle properties are assumed to be constant over particle size sections and (2) the modal approach in which the size distribution is approxi mated by several modes and particle properties are assumed to be uniform in each mode. The sectional approach is accurate for coagulation and can reproduce the major characteristics of the evolution of the particle size distribution for condensa tional growth with the moving-center and hybrid algorithms. For coagulation and condensational growth, the modal approach provides more accurate results when the standard deviations of the modes are allowed to vary than it does when they are fixed. Predictions of H₂SO₄ nucleation rates are highly sensitive to environ mental variables and simulation of relative rates of condensation on existing particles and nucleation is a preferable approach. Explicit treatment of mass transfer is recommended for cases where volatile species undergo different equilib rium reactions in different particle size ranges (e.g., in the presence of coarse salt particles). The results of this study provide useful information for use in selecting algorithms to simulate aerosol dynamics in air quality models and for improving the accuracy of existing algorithms.     

Coagulation of highly concentrated aerosols

A number of material synthesis processes such as flame, plasma and laser ablation have been developed for production of films and powders at low pressure and high temperature. At these conditions particle growth typically takes place by coagulation in the free molecule and transition regimes. As economic manufacturing of these materials favors operation at high particle concentrations, classic coagulation theory may not be sufficient to describe the ensuing aerosol dynamics, especially if fractal-like particles are formed. The coagulation rate of highly concentrated, polydisperse aerosols is investigated here from the free molecule to the continuum regime by solving the corresponding Langevin dynamics (LD) equations. The LD simulations are validated by monitoring the attainment of the self-preserving size distribution (SPSD) for dilute particle volume fractions, φ_s, below 0.1%. High particle concentrations in the free molecule regime lead to deviations of the aerosol dynamics from the kinetic theory of gases especially during instantaneous coalescence (completely inelastic particle–particle collisions) resulting in slower coagulation rates and slightly narrower SPSDs than in conventional dilute aerosols. In the transition regime, the coagulation rate of highly concentrated aerosols is progressively higher than that for dilute aerosols as growing particles enter the continuum regime where coagulation rates are 2–30 times higher than that of classic Smoluchowski theory. At high particle concentrations (φ_s>1%), a SPSD is approached (σ_g,n=1.42) that does not exhibit the characteristic minimum at the transition regime of dilute aerosols. A relationship is developed for the aerosol coagulation rate of highly concentrated aerosols from the free molecule to continuum regime.     

Differences in estimates of size distribution of beryllium powder materials using phase contrast microscopy, scanning electron microscopy, and liquid suspension counter techniques

Accurate characterization of the physicochemical properties of aerosols generated for inhalation toxicology studies is essential for obtaining meaningful results. Great emphasis must also be placed on characterizing particle properties of materials as administered in inhalation studies. Thus, research is needed to identify a suite of techniques capable of characterizing the multiple particle properties (i.e., size, mass, surface area, number) of a material that may influence toxicity. The purpose of this study was to characterize the morphology and investigate the size distribution of a model toxicant, beryllium. Beryllium metal, oxides, and alloy particles were aerodynamically size-separated using an aerosol cyclone, imaged dry using scanning electron microscopy (SEM), then characterized using phase contrast microscopy (PCM), a liquid suspension particle counter (LPC), and computer-controlled SEM (CCSEM). Beryllium metal powder was compact with smaller sub-micrometer size particles attached to the surface of larger particles, whereas the beryllium oxides and alloy particles were clusters of primary particles. As expected, the geometric mean (GM) diameter of metal powder determined using PCM decreased with aerodynamic size, but when suspended in liquid for LPC or CCSEM analysis, the GM diameter decreased by a factor of two (p < 0.001). This observation suggested that the smaller submicrometer size particles attached to the surface of larger particles and/or particle agglomerates detach in liquid, thereby shifting the particle size distribution downward. The GM diameters of the oxide materials were similar regardless of sizing technique, but observed differences were generally significant (p < 0.001). For oxides, aerodynamic cluster size will dictate deposition in the lung, but primary particle size may influence biological activity. The GM diameter of alloy particles determined using PCM became smaller with decreasing aerodynamic size fraction; however, when suspended in liquid for CCSEM and LPC analyses, GM particle size decreased by a factor of two (p < 0.001) suggesting that alloy particles detach in liquid. Detachment of particles in liquid could have significance for the expected versus actual size (and number) distribution of aerosol delivered to an exposure subject. Thus, a suite of complimentary analytical techniques may be necessary for estimating size distribution. Consideration should be given to thoroughly understanding the influence of any liquid vehicle which may alter the expected aerosol size distribution.     

A Bimodal Integral Solution of the Dynamic Equation for an Aerosol Undergoing Simultaneous Particle Inception and Coagulation

A model is developed from the general aerosol dynamic equation, using a bimodal integral formulation that includes particle formation and growth by coagulation in the free molecular regime. The particle inception mode accounts for the introduction of newly formed particles which, through coagulative collisions with one another, constitute the source of the particles in the growth mode. A numerical solution for the system of the first three moments of the particle volume distribution function is discussed, under the assumption of a logarithmic-normal behavior of the two modes of the size distribution function. The bimodal integral solution is subject to a detailed comparison with the MAEROS sectional model for the case of an aerosol that undergoes free molecular coagulation occurring simultaneously with particle formation by a Gaussian source pulse, under flamelike conditions.