Mark R. Stolzenburg

An Ultrafine Aerosol Condensation Nucleus Counter

The development of a condensation nucleus counter (CNC) for detecting ultrafine aerosol (UFA) particles (particle diameter ≤20 nm) is described here. This instrument is designed specifically for high-efficiency detection and counting of ultrafine particles. It is a modified version of the TSI model 3020 continuous flow, single-particle-counting condensation nucleus counter with sequential saturator and condenser. Design modifications incorporating aerosol sheathing techniques have minimized inlet sampling losses and optimized nucleus detection efficiency. Overall counting efficiency for the UFACNC is theoretically predicted including inlet sampling, nucleus activation, and droplet detection efficiencies. The theory was experimentally verified for low concentration, mono-disperse NaCl aerosols in the 2 to 15 nm particle diameter range. The UFACNC has a counting efficiency of > 70% for particles down to 3.5 nm in diameter. Below this size counting efficiency drops sharply to zero at about 2.6 nm with 50% ef...

On-road measurement of fine particle and nitrogen oxide emissions from light- and heavy-duty motor vehicles

Abstract An updated assessment of fine particle emissions from light- and heavy-duty vehicles is needed due to recent changes to the composition of gasoline and diesel fuel, more stringent emission standards applying to new vehicles sold in the 1990s, and the adoption of a new ambient air quality standard for fine particulate matter (PM2.5) in the United States. This paper reports the measurement of emissions from vehicles in a northern California roadway tunnel during summer 1997. Separate measurements were made of uphill traffic in two tunnel bores: one bore carried both light-duty vehicles and heavy-duty diesel trucks, and the second bore was reserved for light-duty vehicles. Ninety-eight percent of the light-duty vehicles were gasoline-powered. In the tunnel, heavy-duty diesel trucks emitted 24, 37, and 21 times more fine particle, black carbon, and sulfate mass per unit mass of fuel burned than light-duty vehicles. Heavy-duty diesel trucks also emitted 15–20 times the number of particles per unit mass of fuel burned compared to light-duty vehicles. Fine particle emissions from both vehicle classes were composed mostly of carbon; diesel-derived particulate matter contained more black carbon (51±11% of PM2.5 mass) than did light-duty fine particle emissions (33±4%). Sulfate comprised only 2% of total fine particle emissions for both vehicle classes. Sulfate emissions measured in this study for heavy-duty diesel trucks are significantly lower than values reported in earlier studies conducted before the introduction of low-sulfur diesel fuel. This study suggests that heavy-duty diesel vehicles in California are responsible for nearly half of oxides of nitrogen emissions and greater than three-quarters of exhaust fine particle emissions from on-road motor vehicles.

On the sensitivity of particle size to relative humidity for Los Angeles aerosols

A TDMA system (Tandem Differential Mobility Analyzer; Rader D.J. and McMurry P.H. J. Aerosol Sci. 17, 771–787, 1986) was used to measure the sensitivity of particle size to relative humidity for monodisperse Los Angeles aerosols. Measurements were made at Claremont, CA on 13 days between 19 June and 3 September 1987, in conjunction with the Southern California Air Quality Study (SCAQS). The particle sizes that were studied ranged from 0.05 μm to 0.5 μm diameter at ambient relative humidity (typically 45–65%). The data provide clear evidence that these atmospheric aerosols were externally mixed. Monodisperse ambient aerosols were often found to split into nonhygroscopic (no water uptake) and hygroscopic portions when humidified. An average of 30% of the particles in the 0.2–0.5 μm range were nonhygroscopic. However, the proportion of the particles that was nonhygroscopic varied considerably from day to day and was, on occasion, as high as 70–80% of the particles. There was no clear evidence for nonhygroscopic 0.05 μm particles, but the data are not definitive on this point. The data also show that for the hydrophilic aerosol fraction, the larger particles (0.4–0.5 μm) grew more when humidified than did smaller particles (0.05–0.2 μm). As relative humidities were increased from 50% to 90%, particle diameters grew by average factors of 1.46 ±0.02 (for 0.5 μm particles), 1.49 ± 0.08 (0.4 μm), 1.19 ± 0.08 (0.2 μm) and 1.12 ± 0.05 (0.05 μm). Similarly, when particles were dried from 50% RH to 6–10% RH, particle diameters changed by factors ranging from 0.94 ± 0.03 (0.5 μm) to 0.98 ± 0.01 (0.05 μm).

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.

Effect of Working Fluid on Sub-2 nm Particle Detection with a Laminar Flow Ultrafine Condensation Particle Counter

The effect of working fluid on size-dependent activation efficiencies with the laminar flow ultrafine condensation particle counter described by Stolzenburg and McMurry (1991) was studied theoretically and experimentally. Criteria considered include tendency to avoid homogeneous nucleation within the condenser and toxicity. The working fluids that were identified have vapor pressures below that of butanol, so particles grow to smaller sizes and are more difficult to detect optically. Therefore we use a second, conventional CPC as a “booster” to grow particles to a detectable size. Experiments were performed to obtain the size- and material-dependent activation efficiencies for ethylene glycol, diethylene glycol, propylene glycol, oleic acid, and DOS. Using diethylene glycol and oleic acid, values of the 50% activation efficiency diameter, Dp50 , for negatively charged particles generated by evaporating sodium chloride, ammonium sulfate, and silver were < 1.2 (< 0.8) nm, 1.4–1.5 (1.0–1.2) nm, and 1.9–2.0 (1.5) nm as mobility (mass) diameter, respectively. The stability of the UCPC for long-term operation using ethylene glycol and propylene glycol as working fluids was tested by monitoring the instruments response to silver particles having size near Dp50 in an air stream at 40–45% relative humidity. The performance was steady (±3%) for several days indicating the instrument performs stably during unattended operation for realistic atmospheric sampling conditions.

Equations Governing Single and Tandem DMA Configurations and a New Lognormal Approximation to the Transfer Function

The basic equations governing the responses of single and tandem differential mobility analyzer (DMA) systems are summarized. Particle diffusion within the DMA resulting in broadening of the transfer function is included in this analysis. For tandem DMA (TDMA) work, a given particle diameter exiting the first DMA is modeled in the following conditioner as growing into a multi-modal lognormal distribution before entering the second DMA. Approximations and solution techniques for both single and tandem DMA systems are discussed. A new lognormal approximation to the DMA transfer function is introduced leading to a simple lognormal form for the TDMA response function. The maximum absolute error of the transfer function is 0.10 at 200 nm in the range plus or minus one and a half standard deviations of the lognormal fit. It is 0.035 at 3 nm in the range plus or minus two standard deviations of the lognormal fit. The maximum fractional error in the calculated TDMA response is no more than 0.08 at 200 nm and 3 nm in the range plus or minus one standard deviation of the lognormal fit.

A Method for Particle Size Amplification by Water Condensation in a Laminar, Thermally Diffusive Flow

A new method is presented for the enlargement of particle size through condensation of water vapor in a laminar, thermally diffusive flow. The method involves the introduction of an air flow at temperature T i into a wet-walled tube at a temperature Tw > Ti . This approach yields higher supersaturation values than either mixing or cold-walled condensers when operating between the same temperature extremes. Model results for the saturation profiles within the condensing region show that the peak supersaturations are reached along the centerline of the flow, and that the activation efficiency curves are steeper for large temperature differences when the cutpoint diameter is smaller. Experiments conducted with three types of aerosol, oleic acid (a water-insoluble oil), a mixture of oxalic acid and sulfate, and with ambient laboratory aerosol confirmed that condensational growth is achieved with this approach, although experimental cutpoints are somewhat higher than predicted for wettable particles.

Mie Theory Evaluation of Species Contributions to 1990 Wintertime Visibility Reduction in the Grand Canyon

Contributions of the major fine particle species to light scattering were evaluated using Mie theory from measurements of sizeresolved chemistry and particle hygroscopicity obtained during the 1990 NGS Visibility Study at Hopi Point, Grand Canyon, from January 9, 1990 through March 31, 1990. It was found that scattering efficiencies of participate carbon mass ranged from 1.5 to 8 m2 per gram of carbon particle mass (assumed equal to 1.4 times carbon mass), with an average value of 5.4 ± 1.5 m2/g. Sulfur size distributions, which are available for the entire 80-day study, show that sulfate scattering efficiencies depend on both relative humidity and on median particle size, and that “dry” (RH <60 percent) sulfur scattering efficiencies range from about 1.5 to 4.5 m2 per gram of ammonium sulfate. This range reflects the wide variability in median sulfur particle size (0.07 to 0.66 urn) that was observed during the study. For the 20-day period during which size distribution data for the major fine particle s...

Intercomparison of near real time monitors of PM2.5 nitrate and sulfate at the U.S. Environmental Protection Agency Atlanta Supersite

[1] Five new instruments for semicontinuous measurements of fine particle (PM2.5) nitrate and sulfate were deployed in the Atlanta Supersite Experiment during an intensive study in August 1999. The instruments measured bulk aerosol chemical composition at rates ranging from every 5 min to once per hour. The techniques included a filter sampling system with automated water extraction and online ion chromatographic (IC) analysis, two systems that directly collected particles into water for IC analysis, and two techniques that converted aerosol nitrate or sulfate either catalytically or by flash vaporization to gaseous products that were measured with gas analyzers. During the one-month study, 15-min integrated nitrate concentrations were low, ranging from about 0.1 to 3.5 μg m -3 with a mean value of 0.5 μg m -3 . Ten-minute integrated sulfate concentrations varied between 0.3 and 40 μg m -3 with a mean of 14 μg m -3 . By the end of the one-month study most instruments were in close agreement, with r-squared values between instrument pairs typically ranging from 0.7 to 0.94. Based on comparison between individual semicontinuous devices and 24-hour integrated filter measurements, most instruments were within 20-30% for nitrate (∼0.1-0.2 μg m -3 ) and 10-15% for sulfate (1-2 leg m -3 ). Within 95% confidence intervals, linear regression fits suggest that no biases existed between the semicontinuous techniques and the 24-hour integrated filter measurements of nitrate and sulfate;, however, for nitrate, the semicontinuous intercomparisons showed significantly less variability than intercomparisons amongst the 24-hour integrated filters.

Tandem Measurements of Aerosol Properties—A Review of Mobility Techniques with Extensions

When multiple instruments are used in tandem it is possible to obtain more complete information on particle transport and physicochemical properties than can be obtained with a single instrument. This article discusses tandem measurements in which submicrometer particles classified according to electrical mobility are then characterized with one or more additional methods. Measurement combinations that are summarized here include mobility plus mass, aerodynamic (or vacuum aerodynamic) diameter, integrated or multiangle light scattering, composition by single particle mass spectrometry, electron microscopy, and so on. Such measurements enable intercomparisons of different measures of size including mobility diameter, optical size, aerodynamic diameter, volume (for agglomerates and nanowires), length (for nanowires), and mass, even for particles that are morphologically and chemically complex. In addition, the article summarizes the use of tandem techniques to measure various transport properties (e.g., dynamic shape factor, sedimentation speed, diffusion coefficient) and physicochemical properties (e.g., mixing state, shape, fractal dimension, density, vapor pressure, equilibrium water content, composition). In addition to providing an overview of such tandem measurements we describe previously unreported results from several novel tandem measurement methods.