A Fast Scanning Mobility Particle Spectrometer for Monitoring Transient Particle Size Distributions

The Scanning Mobility Particle Spectrometer (SMPS) is a key tool for measuring particle size distribution. The application of the instrument to obtain size distributions throughout a wide range of particle sizes for transient systems, such as motor vehicle emissions, has been limited by the time resolution of the SMPS. In this paper, we present a fast-SMPS (f-SMPS) that utilizes a Radial Differential Mobility Analyzer (rDMA) and a Wixing Condensation Particle Counter (mCPC). The combination of these two components allows for the acquisition of particle size distributions on the time scale of several seconds. The Instrument has an operating range of 5–98 nm and can obtain particle size distributions at rates of up to 0.4 Hz. This paper presents the initial construction and calibration of the instrument followed by its application to several sampling scenarios. Samples from the on-road testing of a heavy-duty diesel (HDD) vehicle demonstrate the utility of this instrument for momtor vehicle emissions measurements as size distributions can now be associated with discrete events taking piace during vehicle onroad operation. For instance, these data indicate the presence of a number peak at 15 nm during transient vehicle operation. Previous work indicates that these particles are associated with the loss of engine lubricating oil.     

Fitting Size Distributions to Optical Particle Counter Data

The theoretical considerations of fitting distributions to aerosol-size spectra derived from optical particle counters are discussed. Based on this, a simple procedure is proposed for fitting the density functions of the commonly used Junge and lognormal distributions, and a special case of the modified gamma distribution. The method uses a generalized linear model to allow for the count statistics of particle sampling.     

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.     

Comparison of Vehicle Exhaust Particle Size Distributions Measured by SMPS and EEPS During Steady-State Conditions

Fast-sizing spectrometers, such as the TSI Engine Exhaust Particle Sizer (EEPS), have been widely used to measure transient particle size distributions of vehicle exhaust. Recently, size distributions measured during different test cycles have begun to be used for calculating suspended particulate mass; however, several recent evaluations have shown some deficiencies in this approach and discrepancies relative to the gravimetric reference method. The EEPS converts electrical charge carried by particles into size distributions based on mobility classification and a specific calibration, and TSI recently released a matrix optimized for vehicle emissions as described by Wang et al. (Submitteda). This study evaluates the performance of the new matrix (soot matrix) relative to the original matrix (default matrix) and reference size distributions measured by a scanning mobility particle sizer (SMPS). Steady-state particle size distributions were generated from the following five sources to evaluate exhaust particulates with various morphologies estimated by mass-mobility scaling exponent: (1) A diesel generator operating on ultralow sulfur diesel, (2) a diesel generator operating on biodiesel, (3) a gasoline direct-injection vehicle operating at two speeds, (4) a conventional port-fuel injection gasoline vehicle, and (4) a light-duty diesel (LDD) vehicle equipped with a diesel particulate filter. Generally, the new soot matrix achieved much better agreement with the SMPS reference for particles smaller than 30 nm and larger than 100 nm, and also broadened the accumulation mode distribution that was previously too narrow using the default matrix. However, EEPS distributions still did not agree with SMPS reference measurements when challenged by a strong nucleation mode during high-load operation of the LDD vehicle. This work quantifies the range of accuracy that can be expected when measuring particle size distribution, number concentration, and integrated particle mass of vehicle emissions when using the new static calibration derived based on the properties of classical diesel soot.

Copyright 2015 American Association for Aerosol Research     

Particle Size Distributions in Calcined Powders

The changes in particle size distributions in bayerite and magnesium hydroxide on calcination are reported. In general, size distributions in calcined powders very closely resemble those obtained before calcination. Theoretical changes in particle volume, and hence in volume equivalent diameter, can be calculated from weight-loss data and corresponding densities. Possible reasons for deviation from the theoretical size reduction ratio are also discussed.     

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.     

Particle Size Distributions for an Office Aerosol

As attention has focused on indoor air quality, it has become important to obtain basic information on the effects of heating, ventilating, and air-conditioning system operating parameters on office aerosols. In addition, it is important to know the particle size distributions (PSDs) in a typical office environment in order to address mitigation strategies. Therefore, this study was undertaken to evaluate the effect of percent outdoor air supplied and occupation level on the PSDs and mass concentrations for a typical office building. The outdoor, return, and supply air streams, as well as hallway air, were sampled using measuring equipment covering particle diameters from below 0.1 to above 3.5 μm. The mass concentrations, when the building was occupled, increased by a factor of approximately 2 when return air was recycled over ventilating with maximum outdoor air. The concentrations when unoccupied were at least as low using minimum outdoor air as those when occupied using maximum outdoor air. As expected, the outdoor air was cleaner than the other streams. The next lowest concentrations were obtained for supply air, then return air, with hallway air showing the highest concentrations. The normalized number distributions were found to have a single mode consistently near 0.13 μm; the volumetric distributions show a peak at 0.3 μm. The influence of the damper setting and occupancy level shows up only in the magnitude of the peaks. The distributions found in the hall and for the air streams showed the same general shapes, but the differences in instrumentation preclude other conclusions.     

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.     

Intercomparisons of Mobility Size Spectrometers and Condensation Particle Counters in the Frame of the Spanish Atmospheric Observational Aerosol Network

Red Española de DMAs Ambientales (REDMAAS), the Spanish network of environmental differential mobility analyzers (DMAs), currently comprises six research groups involved in the measurement of atmospheric aerosol size distributions by means of DMAs. The aim of this network is to guarantee the good quality and comparability of the routine measurements carried out at each location and in diverse environments across Spain. In order to achieve this objective, one of its main activities is the annual intercomparison of mobility size spectrometers used within the network (five units of scanning mobility particle sizers [SMPS] and one ultrafine particle monitor [UFPM]). Here we report the 2main results obtained during the 2010–2012 campaigns, including a study on particle deposition in dryers used in ambient air sampling systems. In general, all instruments showed good performance with deviations in accepted tolerance. The intercomparisons have been proved to be a useful exercise to detect instrument problems, such as incorrect calibrations. DMA calibration checks were performed with polystyrene latex reference particles. Deviations of less than 1% were observed during the first year, which increased 4.7% during the last campaign. Some differences among the responses of different condensation particle counter (CPC) models were encountered, being mainly connected to the intrinsic characteristics of each counter. The comparison of UFPM with CPCs has given good results. The SMPS intercomparisons, especially for particles above 20 nm, have been within +/?15% tolerance. Regarding particle deposition in dryers used in sampling systems, particle penetration was lower than predicted by the recommended model. This result was probably due to the fact that not all the possible mechanisms were considered in the model.

Copyright 2015 American Association for Aerosol Research     

Achieving Size Independent Hit-Rate in Single Particle Mass Spectrometry

Recent improvements in single particle mass spectrometers make it possible to optically detect, size, and characterize the compositions of individual particles with diameters larger than a micron and smaller than 100 nm. In these instruments, two stages of optical detection are used to generate a precisely timed trigger pulse that is used to fire the ion generation laser or lasers. However, experience shows that the wide particle size range results in significant differences in laser trigger timing between small and large particles. If not treated these differences produce an instrument with size dependent hit-rate. In this case the operator is forced to optimize the instrument for the desired size range, while contending with a significantly lower hit-rate for other particle sizes. This article presents an analysis of the phenomenon and demonstrates that the dependence of laser trigger timing on particle size stems from the differences in the particle position within the detection laser beam at the instant of detection. We demonstrate that it is possible to compensate for these differences by generating, for each particle, a laser trigger delay coefficient that is a function of particle's time of flight, i.e., its vacuum aerodynamic size. The study also shows that a single function can be used to eliminate the size bias for particles with a wide range of densities.     

Evolution of Particle Size Distributions due to Turbulent and Brownian Coagulation

The time evolution of particle size distribution due to Brownian and turbulent coagulation (using the kernel of Kruis and Kusters (1997)) was systematically investigated. Using a new definition of dimensionless size distribution parameters based on the geometric mean values, self-preserving particle size distributions for turbulent coagulation were found to exist. The width of such distributions depends on the initial size distribution as well as the turbulence intensity. When starting with submicron aerosols, however, only the turbulence intensity plays a role in determining the final self-preserving form, whereas the initial conditions have no influence. Typically, broad particle size distributions with σ g in the 1.5-1.9 range are obtained. Because of the importance of scavenging by the largest particles in the size distribution, the possibility of developing a "runaway mass" exists, for which some experimental indications in turbulent systems exist.     

Improved Lower Particle Size Limit for Aerosol Time-of-Flight Mass Spectrometry

Laboratory and field tests have shown that electrostatic precharging can lead to a substantial decrease in the flow resistance of fabric filters. For lead smelter dust, the effectiveness of the precharger is dependent on the relative humidity of the suspending gas. For relative humidities below 5%, severe back corona occurs in the precharger, which results in poor particle charging and little improvement in filter performance. For relative humidities between 5% and 40%, little or no back corona occurs, precharging is effective and results in a reduction of up to 60% in the flow resistance of the fabric filter. The operational range of the precharger can be extended to lower relative humidities by cooling the earthed electrode. The improvement in filter performance can be achieved without the precipitation of large quantities of dust in the precharger.     

Particle Size and Optical Properties of Montmorillonite in Suspension

The light absorption spectra of monoionic montmorillonite suspensions with Li, Na, K, Rb, NH₄, Cs, Mg, Ca and Ba as adsorbed ions were studied in the wavelength range 200–800 mμ. Theoretical analysis of the spectra showed that in the visible range, only scattering is responsible for light intensity attenuation. The scattering was found to depend on the type of adsorbed ion and to increase systematically along the series from Li to Ba. This was attributed to increased particle size of the clay caused by parallel plate condensation to form tactoids. A geometrical model of a montmorillonite tactoid was assumed. The general dependence of the properties of such tactoids, and of their suspensions, on the number of plates per tactoid was formulated. Using the measured values of light absorbance index, and the theoretical model, the relative sizes, measured by the number of plates per tactoid, in the different ionic forms were calculated. The relative sizes thus estimated were found to agree favorably with relative sizes calculated from negative adsorption surface area measurements. A typical peak of specific light absorption was observed at 240–245 mμ, for both the suspensions and their clay-free supernatant solutions. Though the compound responsible for this peak is unidentified yet, its quantity in the various suspensions could be roughly estimated. The quantity was found to be negatively correlated with the relative size of the tactoid. It was concluded that the average particle size of montmorillonite in suspension markedly and systematically depends on the type of adsorbed ion. The implications of this finding are discussed.     

Registration Probabilities and Pulse-Height Distributions of Coincidences in Optical Particle Counters

In conventional optical particle counters chains of particles' coincidences may occur as a result of continuous view volume illumination and sampling. Because of these coincidences, probability of the presence of several particles in a view volume given by the well-known Poisson distribution cannot be interpreted as a coincidence registration probability. Particle registration probability distribution accounting for chain coincidences is calculated for optical counters with the first maximum of the counter pulse chosen for counting. Registration probability of the doublets is obtained numerically also for counters with the choice of the global maximum of the counter pulse for counting. Pulse-height probability density functions (pdf) are calculated for square, triangular, and Gaussian pulses. It is shown that pdfs of apparent multiplets are resolved in counters with rectangular response pulses and sufficiently high resolution. However, in counters with any nonrectangular response pulses the coincidences have overlapping pulse height distributions. It is shown that counters with the Gaussian pulses allow measuring 30% higher aerosol concentrations compared with the square pulse counters. Aerosol size distribution distortions invoked by coincidences are estimated.

A method of counter view volume determination using coincidences is suggested.     

Packing and Sintering of Two-Dimensional Structures Made fro Bimodal Particle Size Distributions

Binary mixtures of spheres were used to prepare a variety of two-dimensional structures ranging from ordered to disordered. The extent of particle order was influenced by the size ratio and the concentration of the bimodal constituents. If either the sizes or the concentrations were very different, the structures became phase separated into ordered regions of small spheres and ordered regions of large spheres. Disordered structures were produced when particles were present in equal concentrations and when sizes differed by about 30%. The sintering behavior of these two-dimensional structures was also examined. The domain boundaries in the ordered samples were found to develop into cracks during sintering if the domain size was large. In contrast the disordered structures sintered homogeneously, without the formation of large processing defects.     

The Effect of Particle Size Distributions on the Microstructural Evolution During Sintering

Microstructural evolution and sintering behavior of powder compacts composed of spherical particles with different particle size distributions (PSDs) were simulated using a kinetic Monte Carlo model of solid‐state sintering. Compacts of monosized particles, normal PSDs with fixed mean particle radii and a range of standard deviations, and log‐normal PSDs with fixed mode and a range of skewness values were studied. Densification rate and final relative density were found to be inversely proportional to initial PSD width. Grain growth was faster during the early stages of sintering for broad PSDs, but the final grain sizes were smaller. These behaviors are explained by the smallest grains in the broader PSDs being consumed very quickly by larger neighboring grains. The elimination of the small grains reduces both the total number of necks and the neck area between particles, which in turn reduces the regions where vacancies can be annihilated, leading to slower densification rates. The loss of neck area causes grain growth by surface diffusion to become the dominant microstructural evolution mechanism, leading to poor densification. Finally, pore size was shown to increase with the width of PSDs, which also contributes to the lower densification rates.     

Measurement of Atlanta Aerosol Size Distributions: Observations of Ultrafine Particle Events

As part of EPRI's Aerosol Research Inhalation Epidemiology Study (ARIES), measurements of aerosol size distributions in the 3 nm to 2     

Simulating Particle Size Distributions over California and Impact on Lung Deposition Fraction

Reliable simulations of particle mass size distributions by regional photochemical air quality models are needed in regulatory applications because the U.S. EPA's National Ambient Air Quality Standards specify limits on the mass concentration of particles in a specific size range (i.e., aerodynamic diameter <2.5 μm). Considering the associations between adverse health effects and exposure to ultrafine particles, air quality models may need to accurately simulate particle number size distributions in addition to mass size distributions in future applications. In this study, predictions of particle number and mass size distributions by the Community Multiscale Air Quality model with the standard and an updated emission size distribution are evaluated using wintertime observations in California. Differences in modeled lung deposition fraction for simulated and observed particle number size distributions are also evaluated. Simulated mass size distributions are generally broader and shifted to larger diameters than observations, and observed differences in inorganic and carbon (elemental and organic) distributions are not captured by the model. These model limitations can be reasonably accounted for in regulatory modeling applications. Simulated number size distributions are considerably less accurate than mass size distributions and are difficult to represent in air quality models due to large sub-grid-scale concentration gradients. However, modeled number size distributions are responsive to updates of the emission size distribution, and reasonable simulation of background number size distributions might be possible with an improved treatment of emission size distributions. Modeled lung deposition fractions for simulated number size distributions peak in the same lung region as those for number size distributions observed in the background. However, differences in modeled and observed total number concentrations generally suggest large differences in the total number of deposited particles. Future model development on simulating particle mass size distributions should focus on improving predictions of the mass fraction of particles <2.5 μm. Model development for particle number size distributions should focus on reducing differences in modeled lung deposition for modeled and observed distributions.