The Mass Distribution of Large Atmospheric Particles

This paper describes the results of a study to determine the total mass and the mass distribution of atmospheric aerosols, especially that mass associated with particles greater than 10 μm diameter. This study also determined what fraction of the total aerosol mass a standard high-volume air sampler collects and what fraction and size interval settle out on a dust fall plate. A special aerosol sampling system was designed for this study to obtain representative samples of large airborne particles. A suburban sampling site was selected because no local point sources of aerosols existed nearby. Samples were collected under various conditions of wind velocity and direction to obtain measurements on different types of aerosols.

Study measurements show that atmospheric particulate matter has a bimodal mass distribution. Mass associated with large particles mainly ranged from 5 to 100 μm in size, while mass associated with small particles ranged from an estimated 0.03 to 5 μm in size. Combined, these two distributions produced a bimodal mass distribution with a minimum around 5 μm diameter. The high-volume air sampler was found to collect most of the total aerosol mass, not just that fraction normally considered suspended particulate. Dust fall plates did not provide a good or very useful measure of total aerosol mass. The two fundamental processes of aerosol formation, condensation and dispersion appear to account for the formation of a bimodal mass distribution in both natural and anthropogenic aerosols. Particle size distribution measurements frequently are in error because representative samples of large airborne particles are not obtained. Considering this descrepancy, air pollution regulations should specify or be based upon an upper particle size limit.     

Flow Patterns Upstream of Isokinetic Dust Sampling Probes

In isokinetic sampling from a gas stream it is usually assumed that the flow pattern upstream of the sampling probe is not affected by the presence of the probe. That some probes do seriously affect the gas streamlines is shown by velocity traverses taken with a hot wire anemometer under controlled flow conditions in a wind tunnel. The degree to v/hich the streamlines are affected depends on the wall thickness and taper of the nozzle, the stem diameter, as well as on the size and proximity of sampling accessories in the vicinity of the nozzle. For a probe to cause negligible disturbance under isokinetic conditions it should have a sharp-edged nozzle with little or no outside bevel, and the stem of the probe should be at least 11 stem diameters downstream from the nozzle inlet.     

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (～30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.     

Main particulate matter components in Saxony (Germany)

Aerosol filter samples have been collected nearby the industrialised basin of Leipzig in Saxony (Germany) at the research station Melpitz of the Institut für Troposphärenforschung e.V. (IfT). Time series (1992–1998) and a three year comparison (1995–1997) of two different aerosol filter sampling systems, the Sierra-Andersen-PM 10 high volume sampler (daily sample, PM 10 inlet) and the Rupprecht and Patashnik Co. Inc. Model Partisol 2000 (weekly sample, PM 10 and PM 2.5 inlet) are presented and discussed. The comparison of the different sampling systems and strategies yields small differences between the daily and weekly samples for mass and different ions, which may be influenced by sampling duration and flow rates. A general trend of change in aerosol composition was observed: Soot and Sulphate concentrations decreased whereas Nitrate and Ammonium concentrations increased. During summers the mass of coarse particles is higher than in other seasons. One reason could be found in the occurence of longer periods of dry ground surfaces enabling reemission of crustal and biological material. The time series have been integrated in a longer historical aerosol mass trend for Saxony and do show a good agreement. Since 1990 a significant downward trend in gravimetric mass concentration was found.     

Interpretation of Meteorological Pollutant Roses in Areas Subject to Nocturnal Drainage Winds

The composition of aerosol particle products formed from the photochemical reaction of terpenes with NO_x and the chemical reaction of terpenes with ozone was determined using direct insertion probe/high resolution mass spectrometry. Samples of the aerosol particles generated from these gas phase reactions were collected on stainless steel disks using a specially-designed impactor. The samples were analyzed using computer-controlled high resolution mass spectrometry. The photochemical reaction of limonene with NO_x produced more than 30 reaction products in the aerosol phase. The major products identified included aldehydes, alcohols, acids, peroxides, and nitrate esters of alcohols, acids, and peroxides. In addition, there was evidence of dimeric and possibly trimeric reaction products. The composition of aerosol particle products formed from the dark reaction of ozone with limonene was determined and found similar to those products generated in the photochemical reaction, excluding the nitrated species. Aerosol concentrations were monitored using nephelometry which indicated a conversion of terpene to aerosol of 50% or greater for both the limonene and terpinolene reaction systems. The results show that direct insertion probe high resolution mass spectrometric technique has the capability for determining the composition of very polar and high molecular weight materials in aerosol particles. The composition of terpene aerosol particle products and the mass spectral data obtained from their analysis can be used in further studies to determine the importance of terpene aerosol particle formation in ambient air.     

Studies on sampling methods for PCDDs and PCDFs in stack emission

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emission exist both as vapor and sorbed onto the surface of particles. The partition between the two phases is of a dynamic nature and changes rapidly with temperature. When monitoring stack emissions, a sampling method must be used that efficiently collects both phases as well as any condensation aerosol formed in the sampling train. In this study, the two sampling methods used in Sweden, the cooled probe polyurethane foam plug (PUFP) sampling train and the sampling train recommended by the Swedish Environmental Protection Board has been tested for particle collection ability. The results show that an aerosol filter has to be introduced after the condensor in order to collect particle bound PCDDs and PCDFs efficiently.     

Composition and mixing state of the urban background aerosol in the Rhein-Main area (Germany)

Size-resolved aerosol particle samples in the size range 0.1–10 μm aerodynamic diameter were collected in the years 2003 and 2004 at an urban background station in Mainz, Germany. Size, morphology, chemical composition and mixing state of more than 5400 individual particles of 7 selected sampling days were analyzed in detail by scanning electron microscopy and energy-dispersive X-ray microanalysis. In addition, transmission electron microscopy, aerosol mass spectrometry and atomic force microscopy were applied to obtain detailed information about the mixing state of the particles. The fine particle fraction (diameter<1 μm) is always dominated by complex secondary aerosol particles (⩾90% by number) independent from air mass origin. These particles are complex internal mixtures of ammonium and sodium sulfates, nitrates, and organic material. Between 20% and 40% of the complex secondary aerosol particles contain soot inclusions. The composition of the coarse particle fraction (>1 μm diameter) is strongly dependant on air mass history with variable abundances of complex secondary aerosol particles, aged sea salt, silicates, silicate mixtures, calcium sulfates, calcium sulfate/carbonate mixtures, calcium nitrate/carbonate mixtures, biological particles, and external soot.The dominance of complex secondary aerosol particles shows that reduction of the precursor gases is a major goal for successful reduction strategies for PM₁₀.     

Real-time measurements of the chemical composition of size-resolved particles during a Santa Ana wind episode,California USA

Size-resolved particle composition, mass and number concentrations, aerosol scattering coefficients, and prevailing meteorological conditions were measured at the Ellen Browning Scripps Memorial Pier located in La Jolla, California on 15 December 1998. Aerosol particles were sampled using a field transportable aerosol time-of-flight mass spectrometer, allowing for the continuous detection and characterization of single particles from a polydisperse sample. An extensive and rapid change in the chemical composition of aerosol particles with aerodynamic diameters between 1.0 and 2.5 μm has been observed during the onset of a Santa Ana Winds condition. Coincident with the observed change in meteorological conditions, a substantial decrease in sea salt particles corresponds to an increase in dust and carbon-containing particles. This paper examines observations of the rapid changes occurring in the chemical composition of single aerosol particles and demonstrates the new types of information that can be obtained by measuring single particle size and composition with high temporal resolution.     

Study on the effect of iron on PM10 formation and design of a particle-generating system using a cocentric diffusion burner flame

Iron pentacarbonyl was added to a cocentric diffusion burner flame burning a mixture of acetylene and ethylene in a co-flowing stream of air. Samples of aerosols and gaseous species were collected within the flames and above the flames with filters and a sampling bottle, and soot volume fraction through the flame was calculated with laser light extinction measurements. Aerosol was isokinetically collected in the inhalation chamber to measure particle concentration and size distribution. Laser extinction measurement showed that iron (Fe) gave an effect on soot formation process and scanning electron microscopy of the aerosol sample showed that soot particle size for the Fe-doped flame was relatively smaller than that of non-Fe-doped flame. Transmission electron microscopy results indicated that Fe species were separated from the soot at the downstream flame. Particles of the soot and Fe mixture could be generated continuously, and the concentration was kept constant under a given experimental condition using the cocentric diffusion flame burner. The mass loading variation for each target concentration (i.e., 100, 200, and 400 microg/m3) in the inhalation chamber was less than +/-5% during 10 hr. This particle-generating burner system could be used effectively for a bioassay test to evaluate risk     

Performance Characteristics of PM10 Samplers under Calm Air Conditions

ABSTRACT

The size range of airborne particles that is closely related to specific deposition regions in the human respiratory tract and excess lung burden of these deposited particles is associated with disease. Size-selective sampling, therefore, needs to be performed to assess the related health risks. Performance criteria applied to these samplers must be well characterized in order to provide accurate and reliable results. The PM₁₀ samplers that have been used in place of the total suspended particulate samplers for the collection of ambient air particles are more relevant to potential inhalation hazards. In order to be certified, a PM₁₀ sampler must meet reliable performance specifications, primarily the aerosol penetration test with liquid and solid particles in a wind tunnel (wind speeds of 2, 8, and 24 km/hr). This testing is intended to assure reasonable accuracy in aerosol measurements. However, the sampler performance under calm air conditions has not been well studied.

In the present study, the sampling heads of three devices—the Harvard impactor, the Personal Environmental Monitor (PEM), and the Sierra Andersen model 241 dichotomous sampler PM₁₀ inlet head—were tested for aerosol separation efficiency. With the consideration of bias and imprecision of the measurements, five specimens of each type of sampler were chosen for performance testing, repeating the tests 5 times for each specimen. An ultrasonic atomizing nozzle was used to nebulize potassium sodium tartrate tetrahydrate and dioctyl phthalate particles as the solid and liquid challenge aerosols, respectively. The aerosol number concentrations and size distributions upstream and downstream of the samplers were measured by using an aerosizer calibrated against a settling velocity chamber. The results showed that among the samplers tested, the dichotomous sampler PM₁₀ inlet head had the best fit to the PM₁₀ convention, while the other two samplers not only appeared to have a steeper separation-curve slope but also had significant particle bounce when challenged with solid particles. Analysis of variance also confirmed the superiority of the dichotomous samplers. Surface-coating with oil or grease greatly reduced the problem of particle bounce.     

Particle-Molecule Collection by Sonic Flow Impingers

The information presented in this paper is directed to those industrialists and researchers interested in molecule and near micron and submicron particle sampling by a convenient, inexpensive, and sufficiently accurate method. The use of two sonic flow impingers in series is predicted to collect 98-99% of a phosphoric acid aerosol having a mass median diameter of 0.7 p. The first impinger of a new design is shown, in field sampling, to collect simultaneously 90-98% of the aerosol and 95% of molecular fluoride compounds. On the same aerosol, the standard Greenburg-Smith impinger shows a low collection performance, less than 50% at 1 cfm and 65% at sonic velocity. The use of a first impinger at sonic flow greatly simplifies sampling procedures by eliminating the need for a test meter and associated pressure and temperature measurements. Also, for small particle sizes isokinetic sampling is not necessary and sampling line losses by deposition are shown to be less than 1%. The low initial cost of the sampling units and the low manpower requirements for setting up and supervising sampling make possible the taking of a number of samples sufficient to establish emissions over extended intervals of time. The equipment is especially suited to locations having multiple emission sources, or for locations requiring simultaneous sampling of many points.     

Performance characteristics of PM10 samplers under calm air conditions

The size range of airborne particles that is closely related to specific deposition regions in the human respiratory tract and excess lung burden of these deposited particles is associated with disease. Size-selective sampling, therefore, needs to be performed to assess the related health risks. Performance criteria applied to these samplers must be well characterized in order to provide accurate and reliable results. The PM10 samplers that have been used in place of the total suspended particulate samplers for the collection of ambient air particles are more relevant to potential inhalation hazards. In order to be certified, a PM10 sampler must meet reliable performance specifications, primarily the aerosol penetration test with liquid and solid particles in a wind tunnel (wind speeds of 2, 8, and 24 km/hr). This testing is intended to assure reasonable accuracy in aerosol measurements. However, the sampler performance under calm air conditions has not been well studied. In the present study, the sampling heads of three devices--the Harvard impactor, the Personal Environmental Monitor (PEM), and the Sierra Andersen model 241 dichotomous sampler PM10 inlet head--were tested for aerosol separation efficiency. With the consideration of bias and imprecision of the measurements, five specimens of each type of sampler were chosen for performance testing, repeating the tests 5 times for each specimen. An ultrasonic atomizing nozzle was used to nebulize potassium sodium tartrate tetrahydrate and dioctyl phthalate particles as the solid and liquid challenge aerosols, respectively. The aerosol number concentrations and size distributions upstream and downstream of the samplers were measured by using an aerosizer calibrated against a settling velocity chamber. The results showed that among the samplers tested, the dichotomous sampler PM10 inlet head had the best fit to the PM10 convention, while the other two samplers not only appeared to have a steeper separation-curve slope but also had significant particle bounce when challenged with solid particles. Analysis of variance also confirmed the superiority of the dichotomous samplers. Surface-coating with oil or grease greatly reduced the problem of particle bounce.     

Identification of sources of Phoenix aerosol by positive matrix factorization

Chemical composition data for fine and coarse particles collected in Phoenix, AZ, were analyzed using positive matrix factorization (PMF). The objective was to identify the possible aerosol sources at the sampling site. PMF uses estimates of the error in the data to provide optimum data point scaling and permits a better treatment of missing and below-detection-limit values. It also applies nonnegativity constraints to the factors. Two sets of fine particle samples were collected by different samplers. Each of the resulting fine particle data sets was analyzed separately. For each fine particle data set, eight factors were obtained, identified as (1) biomass burning characterized by high concentrations of organic carbon (OC), elemental carbon (EC), and K; (2) wood burning with high concentrations of Na, K, OC, and EC; (3) motor vehicles with high concentrations of OC and EC; (4) nonferrous smelting process characterized by Cu, Zn, As, and Pb; (5) heavy-duty diesel characterized by high EC, OC, and Mn; (6) sea-salt factor dominated by Na and Cl; (7) soil with high values for Al, Si, Ca, Ti, and Fe; and (8) secondary aerosol with SO4(-2) and OC that may represent coal-fired power plant emissions. For the coarse particle samples, a five-factor model gave source profiles that are attributed to be (1) sea salt, (2) soil, (3) Fe source/motor vehicle, (4) construction (high Ca), and (5) coal-fired power plant. Regression of the PM mass against the factor scores was performed to estimate the mass contributions of the resolved sources. The major sources for the fine particles were motor vehicles, vegetation burning factors (biomass and wood burning), and coal-fired power plants. These sources contributed most of the fine aerosol mass by emitting carbonaceous particles, and they have higher contributions in winter. For the coarse particles, the major source contributions were soil and construction (high Ca). These sources also peaked in winter.     

Sampling at controlled relative humidity with a cascade impactor

The design and function of a device that regulates the relative humidity of an ambient aerosol sample is described. We use this RH controller upstream of MOUDI impactors to permit sampling at relative humidities in the 70–80% range. Humidity control is achieved by allowing the aerosol to approach equilibrium with a saturated salt solution. Benefits to sampling with impactors in this relative humidity range include greatly reduced bounce of fine, hygroscopic particles, minimal flow-induced sizing errors, and minimization of uncertainties in measured size distributions due to diurnal variations in relative humidity during sampling. Data from field measurements in a humid environment (Look Rock, TN) and arid environments (Las Vegas, NV and Meadview, AZ) are discussed.     

Identification of Sources of Phoenix Aerosol by Positive Matrix Factorization

ABSTRACT

Chemical composition data for fine and coarse particles collected in Phoenix, AZ, were analyzed using positive matrix factorization (PMF). The objective was to identify the possible aerosol sources at the sampling site. PMF uses estimates of the error in the data to provide optimum data point scaling and permits a better treatment of missing and below-detection-limit values. It also applies nonnegativity constraints to the factors. Two sets of fine particle samples were collected by different samplers. Each of the resulting fine particle data sets was analyzed separately. For each fine particle data set, eight factors were obtained, identified as (1) biomass burning characterized by high concentrations of organic carbon (OC), elemental carbon (EC), and K; (2) wood burning with high concentrations of Na, K, OC, and EC; (3) motor vehicles with high concentrations of OC and EC; (4) nonferrous smelting process characterized by Cu, Zn, As, and Pb; (5) heavy-duty diesel characterized by high EC, OC, and Mn; (6) sea-salt factor dominated by Na and Cl; (7) soil with high values for Al, Si, Ca, Ti, and Fe; and (8) secondary aerosol with SO₄ ^-2 and OC that may represent coal-fired power plant emissions.

For the coarse particle samples, a five-factor model gave source profiles that are attributed to be (1) sea salt, (2) soil, (3) Fe source/motor vehicle, (4) construction (high Ca), and (5) coal-fired power plant. Regression of the PM mass against the factor scores was performed to estimate the mass contributions of the resolved sources. The major sources for the fine particles were motor vehicles, vegetation burning factors (biomass and wood burning), and coal-fired power plants. These sources contributed most of the fine aerosol mass by emitting carbonaceous particles, and they have higher contributions in winter. For the coarse particles, the major source contributions were soil and construction (high Ca). These sources also peaked in winter.     

São Paulo Aerosol Characterization Study

Abstract

The São Paulo Metropolitan area (SPMA) is characterized as having one of the worst air pollution problems in Brazil,with frequent violations of air quality standards for particulate matter. This paper presents the results of a eceptor model source apportionment study carried out to develop a quantitative database on which a control strategy could be developed. The study was conducted in four sites with distinct land uses. Fine, coarse (CP), and total suspended particles (TSP) samples were collected on Teflon and glass filters and analyzed by x-ray fluorescence XRF), ion chromatography, and thermal evolution. The sources were characterized by similar methodology. Chemical mass balance (CMB) receptor modeling indicated that carbonaceous material plays an important role in the aerosol composition; that the three major source categories contributing to the fine particles are vehicles, secondary carbon, and sulfates; and that the main contributors to CP and TSP are road dust and vehicles. All sampling sites presented the same general pattern in terms of source contribution, although this contribution varied from site to site.     

Impact and growth phenomena observed with sub-micrometer atmospheric aerosol particles collected on polished silicon at low coverage

The processes occurring during the initial stages of size-selected sampling of atmospheric aerosol matter were explored by means of high-resolution scanning electron microscopy and energy dispersive X-ray spectrometry. The final four stages of a Berner impactor served to collect particles with aerodynamic diameters between 60 nm and 1 μm on polished silicon substrates at sampling times between 10 s and 16 min. In the single-particle impact regime (fractional coverage below 5%), most of the particles produced circular black tracks, of which 15 to 30% contained cores of carbonaceous nanoparticles. At a fractional coverage above about 10%, initially generated deposits became increasingly active as centres of preferred aerosol collection. As a result, the number of black spots remained almost constant, but the area per spot increased rapidly. At this stage of fractional coverage, structured aerosol matter became visible within large black areas of random shape. The deposits showed clear evidence for the onset of phase separation between carbon nanoparticles and material rich in sulphur, probably a mixture of alkaline and alkaline earth sulphates. After some time of sample storage in air the low-coverage sulphate matter tended to attain a fractal pattern. At a fractional coverage of several hundred per cent, large amorphous or crystalline objects had grown, but 30% or more of the nominal impact area still did not contain any aerosol matter. Moreover, carbon nanoparticles were found to be phase separated from the newly grown, very uniform aerosol material. The observations imply that sub-micrometer aerosol matter collected in impactors has lost memory of the original particle morphology.     

Coarse and fine aerosol source apportionment in Rio de Janeiro,Brazil

The metropolitan area of Rio de Janeiro is one of the twenty biggest urban agglomerations in the world, with 11 million inhabitants in the metropolitan area, and has a high population density, with 1700 hab. km^?2. For this aerosol source apportionment study, the atmospheric aerosol sampling was performed at ten sites distributed in different locations of the metropolitan area from September/2003 to December/2005, with sampling during 24 h on a weekly basis. Stacked filter units (SFU) were used to collect fine and coarse aerosol particles with a flow rate of 17 L min^?1. In both size fractions trace elements were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) as well as water-soluble species by Ion-Chromatography (IC). Also gravimetric analysis and reflectance measurements provided aerosol mass and black carbon concentrations. Very good detection limits for up to 42 species were obtained. Mean annual PM₁₀ mass concentration ranged from 20 to 37 μg m^?3, values that are within the Brazilian air quality standards. Receptor models such as principal factor analysis, cluster analysis and absolute principal factor analysis were applied in order to identify and quantify the aerosol sources. For fine and coarse modes, circa of 100% of the measured mass was quantitatively apportioned to relatively few identified aerosol sources. A very similar and consistent source apportionment was obtained for both fine and coarse modes for all 10 sampling sites. Soil dust is an important component, accounting for 22–72% and for 25–48% of the coarse and fine mass respectively. On the other hand, anthropogenic sources as vehicle traffic and oil combustion represent a relatively high contribution (52–75%) of the fine aerosol mass. The joint use of ICP-MS and IC analysis of species in aerosols has proven to be reliable and feasible for the analysis of large amount of samples, and the coupling with receptor models provided an excellent method for quantitative aerosol source apportionment in large urban areas.     

Carbonaceous aerosol in jet engine exhaust: emission characteristics and implications for heterogeneous chemical reactions

Characteristic parameters of black carbon aerosol (BC) emitted from jet engine were measured during ground tests and in-flight behind the same aircraft. Size distribution features were a primary BC mode at a modal diameter D≈0.045 μm, and a BC agglomeration mode at D<0.2 μm. The total BC number concentration at the engine exit was 2.9×10⁷ cm^-3 with good agreement between model results and in-flight measured number concentrations of non-volatile particles with D⩾0.014 μm. A comparison between total number concentration of BC particles and the non-volatile fraction of the total aerosol at the exit plane suggests that the non-volatile fraction of jet engine exhaust aerosol consists almost completely of BC. In-flight BC mass emission indices ranged from 0.11 to 0.15 g BC (kg fuel)^-1. The measured in-flight particle emission value was 1.75±0.15×10¹⁵ kg^-1 with corresponding ground test values of 1.0–8.7×10¹⁴ kg^-1. Both size distribution properties and mass emission indices can be scaled from ground test to in-flight conditions. Implications for atmospheric BC loading, BC and cirrus interaction and the potential of BC for perturbation of atmospheric chemistry are briefly outlined.     

Programmable Instrument for Controlling Atmospheric Sampling

The University of Arizona and the Pima County Air Pollution Control District conducted a comparison study of the following aerosol samplers: a standard high-volume sampler, a high-volume sampler fitted with a size selective inlet, and a dichotomous virtual impactor. Over sixty samples were collected with the colocated samplers during the first six months of 1981. The concentration (μg/m³) of suspended particulate matter and of sulfate was determined for all the samples, while the concentration of four lithophilic elements (Ca, Fe, Mg, and K) was determined on one third of the samples. Well-defined linear relationships for suspended particulate matter and sulfate were found to exist between each of the three sample collection methods over the concentrafion range encountered in this study. For these samples, there were significant differences in the particulate mass and large particle lithophilic element concentrations collected by each device. However, sulfate values obtained from the three samplers were in excellent agreement with each other. This suggests that the inlet collection efficiency for large particles differs significantly for these three sampling devices. Since the size selective inlet and the dichotomous virtual impactor samplers are each designed for collection of inhalable particles (particles of 15 μm aerodynamic diameter and smaller), they would have been expected to measure approximately equivalent particle mass concentrations. Thus, these differences are important to those interested in selecting a method for measuring airborne particle mass concentrations.