Measurements of Kelvin-Equivalent Size Distributions of Well-Defined Aerosols with Particle Diameters > 13 nm

During the 1979 workshop of the working group on ultrafine aerosols, different experimental techniques for measuring the number concentration and size of ultrafine aerosol particles were compared. In the present paper we report on a comparison of different particle size measuring techniques for ultrafine aerosols. Well-defined monodisperse aerosols with electrical mobility particle diameters ranging from 13 to 100 nm were generated using an electrical aerosol classifier. Kelvin-equivalent size distributions of these aerosols were determined by means of a process-controlled expansion chamber, the size-analyzing nuclei counter (SANC). To this end the considered aerosol was humidified and the number concentration of the droplets growing in the expansion chamber was measured for stepwise increase in supersaturation. At a quite well defined critical supersaturation, a significant increase in the measured droplet concentration, and thus the onset of heterogeneous nucleation, was observed. By means of the Kelvin-Gibbs equation this critical supersaturation is related to the Kelvin-equivalent diameter of the aerosol particles. Measurements were made on NaCl and dioctyl phthalate (DOP) aerosols. For NaCl particles the Kelvin diameter was found to be larger by a factor of about 4 than the electrical mobility diameter, as determined by the electrostatic aerosol classifier. This is explained by the solubility of the NaCl particles. For DOP particles, however, the Kelvin diameter agrees quite well with the electrical mobility diameter. The Kelvin size distributions were found to be quite narrow, indicating a high monodispersity of the generated aerosol as well as a satisfactory size resolution of the SANC. Thus different experimental techniques, based on completely different principles, yielded similar measurement results.     

Measurements of the Size Distribution of Aerosols Produced by Ultrasonic Humidification

Aerosol number and mass distributions produced by an ultrasonic room humidifier and an ultrasonic medical nebulizer were examined in a limited-scale study. Rapid droplet drying occurred at room humidities and under near saturated conditions. A model was tested describing the diameter of dried particles as a function of the dissolved mineral content of the water and the transducer frequency. Water containing 102 mg/L of dissolved minerals in a humidifier with a 1.6 MHz transducer produced droplets with a mass median diameter of 2.9 μm. The number median diameter of particles after drying was computed to be 0.11 μm. The distribution of particles in a nebulizer tube using a NaCl solution was shown to consist of a mixture of dried salt particles and droplets which included coagulated multiplets.     

Determination of Particle Size Distribution of Ultra-Fine Aerosols Using a Differential Mobility Analyzer

The size analysis of ultrafine aerosol particles using a differential mobility analyzer combined with a CNC is discussed from two standpoints: (1) particle loss caused by Brownian diffusion in the analyzer, and (2) data reduction procedure where Fuchs' charging theory is applied. As a result, it has been found that (1) particle loss becomes significant when particle size is smaller than about 15 nm, and (2) a simple and practical data reduction procedure may be used, where the stationary bipolar charge distribution given by Boltzmann's law is modified by using Fuchs' charge distribution in the smaller size range.     

Determination of Arbitrary Moments of Aerosol Size Distributions from Measurements with a Differential Mobility Analyzer

A method to determine arbitrary moments of aerosol size distributions from differential mobility analyzer measurements has been proposed. The proposed method is based on a modification of the algorithm developed by Knutson and Whitby to calculate the moments of electrical mobility distributions. For this modification, the electrical mobility and the charge distribution have been approximately expressed by power functions of the particle diameter. To evaluate the validity of the approximation, we have carried out numerical simulations for typical size distributions. We have found that for typical narrowly distributed aerosols such as polystyrene latex particles and particles that arise in the tandem differential mobility analyzer configuration, the distribution parameters can be accurately determined by this method. For a log-normally distributed aerosol, the accuracy of the distribution parameters determined by this method has been evaluated as a function of the geometric standard deviation. We have also compared the accuracy of the proposed method with other existing methods in the case of the asymmetric Gaussian distribution.     

Measurement of Ambient Aerosols by the Differential Mobility Analyzer Method: Concepts and Realization Criteria for the Size Range Between 2 and 500 nm

Requirements for aerosol spectrometer based on the differential electrical mobility method are deduced from the principles of aerosol classification and concentration determination. Data reduction and method-inherent sources of errors are discussed in detail. Criteria for the components of the arrangement to be used for ambient aerosol size distribution measurements are given with respect to size range, concentration range and time resolution.     

Online Nanoparticle Mass Measurement by Combined Aerosol Particle Mass Analyzer and Differential Mobility Analyzer: Comparison of Theory and Measurements

A combination of a differential mobility analyzer (DMA) and aerosol particle mass analyzer (APM) is used to measure the mass of NIST Standard Reference Materials (SRM®) PSL spheres with 60 and 100 nm nominal diameter, and NIST traceable 300 nm PSL spheres. The calibration PSL spheres were previously characterized by modal diameter and spread in particle size. We used the DMA to separate the particles with modal diameter in a narrow mobility diameter range. The mass of the separated particles is measured using the APM. The measured mass is converted to diameter using a specific density of 1.05. We found that there was good agreement between our measurements and calibration modal diameter. The measured average modal diameters are 59.23 and 101.2 nm for nominal diameters of 60 and 100 nm (calibration modal diameter: 60.39 and 100.7 nm) PSL spheres, respectively. The repeatability uncertainty of these measurements is reported. For 300 nm, the measured diameter was 305.5 nm, which is an agreement with calibration diameter within 1.8%.

The effect of spread in particle size on the APM transfer function is investigated. Two sources of the spread in “mono-dispersed” particle size distributions are discussed: (a) spread due to the triangular DMA transfer function, and (b) spread in the calibration particle size. The APM response function is calculated numerically with parabolic flow through the APM and diffusion broadening. As expected from theory, the calculated APM response function and measured data followed a similar trend with respect to APM voltage. However, the theoretical APM transfer function is narrower than the measured APM response.     

Exhaust Aerosol of a Plasma Enhanced CVD System: I. Size Distribution Measurements

Understanding the origin and fate of plasma-enhanced chemical vapor deposition (CVD) contaminant particles is a critical issue in semiconductor manufacturing in order to improve thin film deposition on wafer surfaces. Several competing external forces will affect a particle's motion in the plasma field prior to either landing on the wafer or entering the exhaust line. Electrical forces dominate during plasma radio frequency (RF) activation creating regions of potential wells. If trapped, the nucleated particles can continue to grow and gain electron charges until gas or ion drag forces can overcome the potential barrier. Mutual electrostatic repulsion between particles can also cause the traps to "leak" out contaminants into the exhaust line. In this way, contaminants formed solely in the plasma volume are hypothesized to possess a distinctive size and charge distribution independent of condensation particles originating from gas compression by the oil-based rotary pump. For these reasons, a novel experimental aerosol sampling system was designed to continuously monitor submicron particles carried during a thin film deposition cycle without disturbing the internal operation of the plasma. Sampling from the plasma enhanced chemical vapor deposition (PECVD) process exhaust gases using an oil-free mechanical piston pump parallel to the main vacuum line is considered to be an effective alternative to in situ probe measurement. Concentration and size distribution data were continuously measured using a condensation nucleus counter and an optical spectrometer. Results show that the particles in the reactor exhaust line are bimodal or made up of fine and coarse sizes divided near 100 nm. Experimental results show the fine fraction increases in the exhaust line after a certain time interval. This delay is hypothesized to be the initial period the nucleated particles were trapped inside the plasma's potential wells. Once trapped, reactor particles can continue to grow in agreement with free molecular coagulation models. A larger particle will experience greater gas drag to eventually overcome the electrical forces. The delay, or critical transport time, depends upon the reactor pressure and plasma power, which also affect the size of the trapping field. The second paper in the series "Exhaust Aerosol of a Plasma Enhanced CVD System" compares a computational charging model of the plasma sheath with experimental charge distribution measurements of contaminant particles carried through the CVD exhaust.     

Retrieval of Aerosol Complex Refractive Index by Combining Cavity Ring Down Aerosol Spectrometer Measurements with Full Size Distribution Information

Cavity ring down aerosol extinction measurements are combined with size distribution measurements to provide a multi-parameter basis for the retrieval of the aerosol complex refractive index. We show that two distinct size distributions of small particles (< 300 nm) suffice to obtain robust convergence of the Mie theory fit of the extinction function. Experiments are performed both for purely scattering and for absorbing aerosol. Thus this method provides a perspective to use cavity ring down aerosol spectroscopy in field and laboratory measurements that often suffer from low particle concentrations and a lack of large particles.     

Comparison of Measured Particle Lung-Deposited Surface Area Concentrations by an Aerotrak 9000 Using Size Distribution Measurements for a Range of Combustion Aerosols

Surface area in addition to mass concentration is increasingly being emphasized as an important metric representing potential adverse health effects from exposure to inhaled particles. Lung-deposited surface area (SA) concentrations for a variety of aerosols: coal, biomass, cigarette, incense, candle, and TiO₂ were measured using an AeroTrak 9000 (TSI Incorporated) and compared with those calculated from number size distributions from a scanning mobility particle sizer (SMPS). Three methodologies to compute the SA concentrations using the International Commission on Radiological Protection's (ICRP) Lung Deposition model and an SMPS were compared. The first method calculated the SA from SMPS size distributions, while the second method used lognormal size distribution functions. A third method generated a closed-form equation using the method of moments. All calculated SMPS SA data against which the measured SA data were compared were generated using the first method only; however, the SA concentrations calculated from each of the three methods demonstrated strong correlations with each other. Overall, results between measured and calculated lung-deposited SA indicated strong positive linear associations (R ² 0.78 - >0.99), moderately dependent on the type of aerosol. In all cases, the measured SA concentrations slightly underestimated those calculated from the SMPS data, with the exception of coal combustion particles. Although some dependency on aerosol material exists, the instrument measuring lung-deposited SA demonstrated consistent reliability across a range of concentrations for a range of materials. For optimal results however, applying a correction factor (CF) before taking the instrument to the field is recommended.

Copyright 2013 American Association for Aerosol Research     

Determination of the Nanoparticle Size Distribution in Media by Turbidimetric Measurements

For incorporation of nanoparticles into matrices, it is necessary to control the particle size distribution during processing. In this paper, a turbidimetric method was applied that uses spectroscopic data to determine the nanoparticle size distribution and, consequently, to control the material properties with a non‐contact measurement method. This method is based on the scattering and absorption of light by the particles. Unlike conventional turbidimetric methods, this method uses not only a few wavelengths but a whole spectral range for evaluation. To determine the distribution parameters, a nonlinear numerical least squares fit routine was established. It was validated by comparing data of water‐silica nanosuspensions with the results from the sedimentation method. The results show that this method is an accurate and easy‐to‐use analysis instrument for the characterization of nanosuspensions, emulsions, and aerosols.     

用激光粒度分析仪检测细粒径SiO2基相变调湿复合材料的粒度分布

以SiO2为载体、棕榈醇-棕榈酸-月桂酸为相变材料,采用溶胶-凝胶法制备细粒径SiO2基相变调湿复合材料,以中位径(d50)为评价指标,采用激光粒度分析仪研究了溶液溶质浓度、超声时间、超声频率及分散介质对材料粒度的影响. 结果表明,激光粒度分析仪可用于检测SiO2基相变调湿复合材料的粒度分布,水对材料的分散效果比乙醇好,以水为分散介质,材料最佳溶质浓度为5~10 g/L,最佳超声时间为15 min以上,最佳超声功率大于400 W.     

Comparison and Combination of Aerosol Size Distributions Measured with a Low Pressure Impactor,Differential Mobility Particle Sizer,Electrical Aerosol Analyzer,and Aerodynamic Particle Sizer

Data from a different mobility particle sizer (DMPS) or an electrical aerosol analyzer (EAA) has been combined with data from an aerodynamic particle sizer (APS) and converted to obtain aerosol mass distribution parameters on a near real-time basis. A low pressure impactor (LPI), a direct and independent measure of this mass distribution, provided information for comparison.

The number distribution of particles within the electrical measurement range was obtained with the DMPS and EAA. Data from the APS for particles greater than that size were used to complete the number distribution. Two methods of obtaining mass distribution parameters from this number data were attempted. The first was to convert the number data, channel by channel, to mass data and then fit a log-normal function to this new mass distribution. The second method was to fit a log-normal function to the combined number distribution and then use the Hatch-Choate equations to obtain mass parameters.

Both the DMPS / APS and the EAA / APS systems were shown to successfully measure aerosol mass distribution as a function of aerodynamic diameter. Careful operation of the measurement equipment and proper data manipulation are necessary to achieve reliable results. A channel-by-channel conversion from number to mass distribution provided the best comparison to the LPI measurement. The DMPS / APS combination furnishes higher-size resolution and accuracy than the EAA / APS system. A small gap was observed in the EAA / APS combined data; however, this did not seem to adversely affect the determination of mass distribution parameters.     

Comment on the Calculation of the Steady-State Charge Distribution on Aerosols < 100 nm by Three Body Trapping Method in a Bipolar Ion Environment

The theory of Fuchs (1963) Fuchs, N. 1963. On the Stationary Charge Distribution on Aerosol Particles in a Bipolar Ionic Atmosphere. Geofis. Pura Appl., 56: 185–192. [Crossref] , [Google Scholar] is widely used for calculation of the steady-state charge distribution on (submicron) aerosol particles in a bipolar ion environment. Hoppel and Frick (1986) Hoppel, W. and Frick, G. 1986. Ion-Aerosol Attachment Coefficients and the Steady-State Charge Distribution on Aerosols in a Bipolar Environment. J. Aerosol Sci., 5: 1–21. [Taylor & Francis Online] , [Google Scholar] and others showed that the Fuchs theory is no longer valid for particle diameters in the order of magnitude of the ionic mean free path. In their 1986 and 1990 papers, Hoppel and Frick published a new calculation method based on the concept of thee-body trapping, which is applicable for small particles down to the size of ions. Some print and procedure mistakes were made in the named publications. Additionally some important calculation information was not given. In this article, the relevant equations are shown, corrected and appended. A recalculation of the charge distributions for small particles based on three-body trapping shows a pronounced difference in comparison to data calculated according to the theory of Fuchs.     

Development and Validation of a Simple Numerical Model for Estimating Workplace Aerosol Size Distribution Evolution Through Coagulation,Settling, and Diffusion

Recent research has indicated that the toxicity of inhaled ultrafine particles may be associated with the size of discrete particles deposited in the lungs. However, it has been speculated that in some occupational settings rapid coagulation will lead to relatively low exposures to discrete ultrafine particles. Investigation of likely occupational exposures to ultrafine particles following the generation of aerosols with complex size distributions is most appropriately addressed using validated numerical models. A numerical model has been developed to estimate the size-distribution time-evolution of compact and fractal-like aerosols within workplaces resulting from coagulation, diffusional deposition, and gravitational settling. Good agreement has been shown with an analytical solution to lognormal aerosol evolution, indicating good compatibility with previously published models. Validation using experimental data shows reasonable agreement when assuming spherical particles and coalescence on coagulation. Assuming the formation of fractal-like particles within a range of diameters led to good agreement between modeled and experimental data. The model appears well suited to estimating the relationship between the size distribution of emitted well-mixed ultrafine aerosols, and the aerosol that is ultimately inhaled where diffusion loses are small.     

Particle Morphology and Density Characterization by Combined Mobility and Aerodynamic Diameter Measurements. Part 2: Application to Combustion-Generated Soot Aerosols as a Function of Fuel Equivalence Ratio

Composition, shape factor, size, and fractal dimension of soot aerosol particles generated in a propane/O₂, flame were determined as a function of the fuel equivalence ratio (φ). Soot particles were first size-selected by a differential mobility analyzer (DMA) and then analyzed by an Aerodyne aerosol mass spectrometer (AMS). The DMA provides particles of known mobility diameter (d_m ). The AMS quantitatively measures the mass spectrum of the nonrefractory components of the particles and also provides the vacuum aerodynamic diam eter (d_va ) corresponding to the particles of known mobility diameter. The measured d_m, d_va , and nonrefractory composition are used in a system of equations based on the formulation presented in the companion article to estimate the particle dynamic shape factor, total mass, and black carbon (BC) content. Fractal dimension was estimated based on the mass-mobility relationship. Two types of soot particles were observed depending on the fuel equivalence ratio. Type 1: for φ < 4 (lower propane/O₂), d_va ; was nearly constant and independent of d_m . The value of d_va increased with increasing φ. Analysis of the governing equations showed that these particles were highly irregular (likely fractal aggregates), with a dynamic shape factor that increased with d_m and φ. The fractal dimension of these particles was approximately 1.7. These particles were composed mostly of BC, with the organic carbon content increasing as φ increased. At φ = 1.85, the particles were about 90% BC, 5% PAH, and 5% aliphatic hydrocarbon (particle density = 1.80 g/cm³). Type 2: for φ > 4 (high propane/O₂), d_va was linearly proportional to d_m . Analysis of the governing equations showed that these particles were nearly spherical (likely compact aggregates), with a dynamic shape factor of 1.1 (versus 1 for a sphere) and a fr actal dimension of 2.95 (3 for a sphere). These particles were composed of about 50% PAH, 45% BC, and 5% aliphatic hydrocarbons (particle density = 1.50 g/cm³). These results help interpret some measurement s obtained in recent field studies.     

Size Distribution and Estimated Respiratory Deposition of Total Chromium,Hexavalent Chromium,Manganese, and Nickel in Gas Metal Arc Welding Fume Aerosols

A laboratory study was conducted to determine the mass of total Cr, Cr(VI), Mn, and Ni in 15 size fractions for mild and stainless steel gas-metal arc welding (GMAW) fumes. Samples were collected using a nano multi orifice uniform deposition impactor (MOUDI) with polyvinyl chloride filters on each stage. The filters were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography. Limits of detection (LODs) and quantitation (LOQs) were experimentally calculated and percent recoveries were measured from spiked metals in solution and dry, certified welding-fume reference material. The fraction of Cr(VI) in total Cr was estimated by calculating the ratio of Cr(VI) to total Cr mass for each particle size range. Expected, regional deposition of each metal was estimated according to respiratory-deposition models. The weight percent (standard deviation) of Mn in mild steel fumes was 9.2% (6.8%). For stainless steel fumes, the weight percentages were 8.4% (5.4%) for total Cr, 12.2% (6.5%) for Mn, 2.1% (1.5%) for Ni and 0.5% (0.4%) for Cr(VI). All metals presented a fraction between 0.04 and 0.6 μm. Total Cr and Ni presented an additional fraction <0.03 μm. On average 6% of the Cr was found in the Cr(VI) valence state. There was no statistical difference between the smallest and largest mean Cr(VI) to total Cr mass ratio (p-value = 0.19), hence our analysis does not show that particle size affects the contribution of Cr(VI) to total Cr. The predicted total respiratory deposition for the metal particles was ～25%. The sites of principal deposition were the head airways (7–10%) and the alveolar region (11–14%). Estimated Cr(VI) deposition was highest in the alveolar region (14%).     

Effect of Rotor Disc Diameter on Holdup,Axial Dispersion and Droplet Size in a Taylor‐Couette Disc Contactor

Application of liquid‐liquid extraction is on a steady rise. Although there are considerable designs of extraction devices, equipment design and optimization is still on the research agenda. Utilization in the biorefinery industry or metallurgy requires robust technologies and equipment. The simple design and stable operation performance of the Taylor‐Couette disc contactor suffices the technical needs for these harsh operation conditions. The effect of different rotor disc diameter on the dispersed phase holdup, axial dispersion, and droplet size was investigated. It was shown that with smaller rotor disc diameter stable operation is still feasible but higher axial backmixing has to be expected.     

Quantification of Hourly Speciated Organic Compounds in Atmospheric Aerosols,Measured by an In-Situ Thermal Desorption Aerosol Gas Chromatograph (TAG)

The Thermal desorption Aerosol Gas chromatograph (TAG) is a recently developed instrument for the in-situ, hourly measurement of speciated organic compounds in atmospheric aerosols. This paper presents a method for the in-field calibration of this instrument, with the objective of providing quantitative concentrations for a large suite of low polarity organic compounds. A new collection and thermal desorption cell was developed that incorporates an injection port for in-situ calibrations with liquid standard mixtures. Two classes of injection standards, instrument tracking and auxiliary, provide the means to calibrate the instrument in the field for a wide range of compounds. A routinely injected tracking standard suite of compounds generates a time-dependent correction of detector drift through the course of a measurement study that accounts for the bulk of the change in response of the TAG instrument. Injection response data for the tracking standard is also used to measure instrument precision and limits of quantitation. Auxiliary standards extend the range of compounds calibrated through use of relative response factors. The accuracy of this in-situ calibration approach is assessed through comparisons of TAG analyzed reference filter punches to published NIST assay values. A subset of compound classes, alkanes and PAHs, are used to illustrate the method and provide a means of reducing an 11-day period of data collected in Riverside, CA during the fall of 2005.     

An Intensive Study of the Size and Composition of Submicron Atmospheric Aerosols at a Rural Site in Ontario,Canada

Atmospheric sampling was conducted at a rural site near Egbert, about 70 km north of Toronto, Ontario, Canada from March 27 to May 8, 2003 to characterize the physical and chemical properties of the ambient aerosol in near real-time. The instrumentation included a tapered element oscillating microbalance (TEOM), an ultrafine condensation particle counter (UCPC), a scanning mobility particle sizer (SMPS), an aerodynamic particle sizer (APS), an aerosol mass spectrometer (AMS), and a particulate nitrate monitor (R&P 8400N) for aerosol measurements. Gas-phase non-methane hydrocarbon compounds (NMHCs) were measured by gas chromatograph-flame ionization detection (GC-FID). Filter samples were also collected for analysis of inorganic ions by ion chromatography (IC). Aerosol properties varied considerably depending upon meteorological conditions and airmass histories. For example, urban and industrial emissions advected from the south strongly influenced the site occasionally, resulting in higher particulate mass with the higher fractions of nitrate and organics. Cleaner northwesterly winds carried aerosols with relatively higher fractions of organics and sulfate. The AMS derived mass size distributions showed that the inorganic species in the particles with vacuum aerodynamic diameters between about 60 nm and 600 nm had mass modal vacuum aerodynamic diameters around 400–500 nm. The particulate organics often exhibited two modes at about 100 nm and 425 nm, more noticeable during fresh pollution events. The small organic mode was well correlated with gas-phase nonmethane hydrocarbons such as ethylbenzene, toluene, and propene, suggesting that the likely sources of small organic particles were combustion related emissions. The particulate nitrate exhibited a diurnal variation with higher concentrations during dark hours and minima in the afternoon. Particulate sulfate and organics showed evidence of photochemical processing with higher levels of sulfate and oxygenated organics in the afternoon. Reasonable agreement among all of the co-located measurements is found, provided the upper size limit of the AMS is considered.