Optical measurements of aerosol size distributions in Great Smoky Mountains National Park: dry aerosol characterization

Aerosol size distributions were measured during the summertime 1995 Southeastern Aerosol and Visibility Study (SEAVS) in Great Smoky Mountains National Park using an Active Scattering Aerosol Spectrometer (ASASP-X) optical particle counter. We present an overview of the experimental method, our data inversion technique, timelines of the size distribution parameters, and calculations of dry accumulation mode aerosol density and refractive index. Aerosol size distributions were recorded during daylight hours for aerosol in the size range 0.1 < Dp < 2.5 microns. The particle refractive index used for the data inversion was calculated with the partial molar refractive index approach using 12-hr measured aerosol chemical composition. Aerosol accumulation mode volume concentrations ranging from 1 to 26 micron 3 cm-3 were observed, with an average of 7 +/- 5 micron 3 cm-3. The study average dry accumulation mode geometric volume median diameter was 0.27 +/- 0.03 micron, and the mean geometric standard deviation was 1.45 +/- 0.06. Using an internally mixed aerosol model, and assuming chemical homogeneity across the measured particle distribution, an average accumulation mode dry sulfate ion mass scattering efficiency of 3.8 +/- 0.6 m2 g-1 was calculated.     

Difficulties inherent to the use of analytic solution of the condensation–evaporation equation for multicomponent aerosols

We present the analytic solution to the problem of multicomponent aerosol evolution due to condensation and/or evaporation of its components. We pose the general equation that governs the evolution of the particle size distributions of each species, and then solve it through the method of characteristic curves. The obtained solution is of interest because it permits an approximate analysis of cases of practical importance without numerical methods. Furthermore, the analytic solutions can be used to validate the numerical methods which, up to now, are only compared with mono-component cases. When all components condense, the obtained solution is valid for all time values. When some of the components evaporate the problem is more complex, due to the fact that no component exists in a negative amount. This suggests the formation of shock waves (high peaks in particle size distribution) and rare-faction waves, which are difficult to handle. Finally, we apply the method to several interesting cases.     

Light scattering characteristics of aerosols as a function of relative humidity: Part I--A comparison of measured scattering and aerosol concentrations using the theoretical models

The Southeastern Aerosol and Visibility Study (SEAVS) was undertaken to characterize the size-dependent composition, thermodynamic properties, and optical characteristics of the ambient atmospheric particles in the southeastern United States. The field portion of the study was carried out from July 15 to August 25, 1995. As part of the study a relative humidity controlled inlet was built to raise or lower the relative humidity to predetermined levels before the aerosol was passed into an integrating nephelometer or particle-sizing device. Five other integrating nephelometers were operated in various configurations, two of which were fitted with a 2.5 microns inlet. Fine particle (< 2.5 microns) samplers were operated to measure concentrations of sulfate, nitrate, and ammonium ions, organic and elemental carbon, and fine soil. Mass size distributions were measured with an eight-stage, single orifice cascade impactor. Four different strategies for estimating scattering were used. First, an externally mixed model with constant specific scattering coefficients, sulfate ion mass interpreted as ammonium bisulfate, and ammonium bisulfate growth as a function of relative humidity, is assumed. Second, an externally mixed aerosol model, assuming constant dry specific scattering but with sulfate ammoniation and associated composition-dependent hygroscopicity explicitly accounted for, is used. Third, an externally mixed aerosol model, but with sulfate ammoniation, associated growth as a function of relative humidity, and sulfate size distributions, is applied. Fourth, an internally mixed aerosol model with measured sulfur size distributions and estimated size distributions for other species is used with the growth characteristics of the mixture being estimated using the Zdanovskii-Stokes-Robinson (ZSR) assumptions. Only ionic species were considered to be hygroscopic. The second, third, and fourth approaches yield similar results with reconstructed scattering comparing quite favorably with measured scattering. Accounting for sulfate ammoniation and associated water uptake was the most important detail in achieving closure between measurements and modeled scattering. In general, differences between estimated scattering, assuming internally or externally mixed models, was small. These same models were used to estimate wet to dry scattering ratios. The R2 for an ordinary least-squares regression between measured and predicted ratios was high (0.71-0.92), and in most cases the scattering ratio was insensitive to modeling assumptions. However, during some sample periods differences between predicted scattering ratios for the different modeling assumptions were as high as 30%.     

A 3-mode parameterization of below-cloud scavenging of aerosols for use in atmospheric dispersion models

Atmospheric aerosols are subject to below-cloud scavenging by precipitation. The scavenging coefficient depends on the aerosol size significantly. The traditional bulk parameterization represents the mean wet scavenging coefficient for the whole aerosol size range. This parameterization significantly overestimates the scavenging of aerosol mass by a heavy rain or a long-duration medium rain. In this study, we present a 3-mode parameterization of the mean scavenging coefficient for each aerosol mode instead of representation for the whole aerosol size range. The new parameterization takes into account the aerosol number size distribution, the rain droplet size distribution and the spectral collision efficiency between the aerosol particle and the rain droplet. Comparing the calculation of mass depletion due to below-cloud scavenging, the 3-mode parameterization agrees well with the size-resolved explicit method. The new parameterization can be easily implemented in atmospheric dispersion models.     

Optical Measurements of Aerosol Size Distributions in Great Smoky Mountains National Park: Dry Aerosol Characterization

ABSTRACT

Aerosol size distributions were measured during the summertime 1995 Southeastern Aerosol and Visibility Study (SEAVS) in Great Smoky Mountains National Park using an Active Scattering Aerosol Spectrometer (ASASP-X) optical particle counter. We present an overview of the experimental method, our data inversion technique, timelines of the size distribution parameters, and calculations of dry accumulation mode aerosol density and refractive index. Aerosol size distributions were recorded during daylight hours for aerosol in the size range 0.1 < Dp < 2.5 u,m. The particle refractive index used for the data inversion was calculated with the partial molar refractive index approach using 12-hr measured aerosol chemical composition. Aerosol accumulation mode volume concentrations ranging from 1 to 26 u,m³ cm^-3 were observed, with an average of 7 ± 5 u,m³ cm^-3. The study average dry accumulation mode geometric volume median diameter was 0.27 ± 0.03 u,m, and the mean geometric standard deviation was 1.45 ± 0.06. Using an internally mixed aerosol model, and assuming chemical homogeneity across the measured particle distribution, an average accumulation mode dry sulfate ion mass scattering efficiency of 3.8 ± 0.6 m² g^-1 was calculated.     

Observations and modelling of aerosol growth in marine stratocumulus—case study

Airborne measurements of the growth of the marine accumulation mode after multiple cycles through stratocumulus cloud are presented. The nss-sulphate cloud residual mode was log-normal in spectral shape and it’s mode radius was observed to progressively increase in size from 0.78 to 0.94 μm over 155 min of air parcel evolution through the cloudy marine boundary layer. The primary reason for this observed growth was thought to result from aqueous phase oxidation of SO₂ to aerosol sulphate in activated cloud drops. An aqueous phase aerosol–cloud-chemistry model was used to simulate this case study of aerosol growth and was able to closely reproduce the observed growth. The model simulations illustrate that aqueous phase oxidation of SO₂ in cloud droplets was able to provide enough additional sulphate mass to increase the size of activated aerosol. During a typical cloud cycle simulation, ≈4.6 nmoles kg^-1_air (0.44 μg m^-3) of sulphate mass was produced with ≈70% of sulphate production occurring in cloud droplets activated upon sea-salt nuclei and ≈30% occurring upon nss-sulphate nuclei, even though sea-salt nuclei contributed less than 15% to the activated droplet population. The high fraction of nss-sulphate mass internally mixed with sea-salt aerosol suggests that aqueous phase oxidation of SO₂ in cloud droplets activated upon sea-salt nuclei is the dominant nss-sulphate formation mechanism and that sea-salt aerosol provides the primary chemical sink for SO₂ in the cloudy marine boundary layer.     

Estimating fine particulate matter component concentrations and size distributions using satellite-retrieved fractional aerosol optical depth: part 2--a case study

We use the fractional aerosol optical depth (AOD) values derived from Multiangle Imaging Spectroradiometer (MISR) aerosol component measurements, along with aerosol transport model constraints, to estimate ground-level concentrations of fine particulate matter (PM2.5) mass and its major constituents in the continental United States. Regression models using fractional AODs predict PM2.5 mass and sulfate (SO4) concentrations in both the eastern and western United States, and nitrate (NO3) concentrations in the western United States reasonably well, compared with the available ground-level U.S. Environment Protection Agency (EPA) measurements. These models show substantially improved predictive power when compared with similar models using total-column AOD as a single predictor, especially in the western United States. The relative contributions of the MISR aerosol components in these regression models are used to estimate size distributions of EPA PM2.5 species. This method captures the overall shapes of the size distributions of PM2.5 mass and SO4 particles in the east and west, and NO3 particles in the west. However, the estimated PM2.5 and SO4 mode diameters are smaller than those previously reported by monitoring studies conducted at ground level. This is likely due to the satellite sampling bias caused by the inability to retrieve aerosols through cloud cover, and the impact of particle hygroscopicity on measured particle size distributions at ground level.     

Variation of the mixing state of Saharan dust particles with atmospheric transport

Mineral dust is an important aerosol species in the Earth’s atmosphere and has a major source within North Africa, of which the Sahara forms the major part. Aerosol Time of Flight Mass Spectrometry (ATOFMS) is first used to determine the mixing state of dust particles collected from the land surface in the Saharan region, showing low abundance of species such as nitrate and sulphate internally mixed with the dust mineral matrix. These data are then compared with the ATOFMS single particle mass spectra of Saharan dust particles detected in the marine atmosphere in the vicinity of the Cape Verde islands, which are further compared with those from particles with longer atmospheric residence sampled at a coastal station at Mace Head, Ireland. Saharan dust particles collected near the Cape Verde Islands showed increased internally mixed nitrate but no sulphate, whilst Saharan dust particles collected on the coast of Ireland showed a very high degree of internally mixed secondary species including nitrate, sulphate and methanesulphonate. This uptake of secondary species will change the pH and hygroscopic properties of the aerosol dust and thus can influence the budgets of other reactive gases, as well as influencing the radiative properties of the particles and the availability of metals for dissolution.     

Comparison of black carbon (BC) aerosols in two urban areas – concentrations and size distributions

In this study, the BC aerosol measured at two very different urban sites is compared in terms of concentration, seasonal variation, and size distribution. During a 14 month study, one impactor sample was performed each month on a day with typical meteorological conditions. One (Vienna) or three (Uji) filter samples were obtained during the sampling time of the impactors. BC concentration in both the filter and impactor samples was analyzed with an optical technique (integrating sphere technique), where a calibration curve obtained from commercial carbon black is used to convert the optical signal to BC mass. Gravimetric mass concentration was measured at both sites. The gravimetric mass size distribution was measured only in Vienna. At both sites, the yearly average of the BC concentration on the sampling days was around 5 μg m⁻³. In Vienna, some seasonal trend with high concentrations during the cold season was observed, while in Uji, no pronounced seasonal trend was found. The BC size distribution in Uji was distinctly bimodal in the submicron size range. Log-normal distributions were fitted through the impactor data. The average BC mass median diameters (MMD) of the two submicron modes were 0.15 and 0.39 μm. Each mode contained about the same amount of BC mass. In Vienna only one submicron BC mode (average MMD 0.3 μm) was found because of the low size resolution of the impactor. An analysis of humidity effects on the MMDs of BC (both sites) and gravimetric mass (Vienna only) indicates that the Vienna aerosol is partly mixed internally with respect to BC, while the Uji aerosol seems to be externally mixed.     

On radiative effects of black carbon and sulphate aerosols

Most aerosol particles, such as sulphate and sea-salt particles, mainly scatter solar radiation, whilst soot (in the form of elemental carbon or “black” carbon, BC) in addition leads to considerable absorption. This scattering and absorption by the aerosol particles constitute the so-called direct aerosol effect. In this paper, we present results from a study of possible direct effects of tropospheric BC and sulphate aerosols, with an emphasis on BC aerosols, along a line from North Africa through Europe into the Arctic. Radiative budgets in a cloud-free atmosphere are estimated. Based on model-calculated distributions of BC and sulphate (provided by Seland and Iversen, 1998) and assumed size distributions of the background aerosol, new size distributions are obtained by adding natural, biomass burning and fossil fuel contributions to the background aerosol. Added nucleation mode particles are assumed externally mixed, whereas added accumulation mode BC and sulphate is internally mixed with the background according to condensational growth and Brownian coagulation theory. Humidity effects are taken into account by use of the Köhler equation. Mie calculations provide the resulting optical parameters, and the forcing is finally estimated by use of a radiative transfer model. A reference run and a series of eleven test-runs are performed to investigate the sensitivity of various assumptions on the contribution to upward TOA irradiance from BC and non-sea-salt sulphate. The tests suggest a high sensitivity to presence of BC and to particle swelling due to humidity. The sensitivity to assumed distribution of BC on particle size is more moderate. The same is true for the vertical resolution and the number concentration of the background aerosol. The effect of mixing organic carbon (OC) internally with biomass burning BC nucleation mode particles is characterized as moderate. The role of OC is, however, still uncertain. The same holds true for the optical thickness of the background atmosphere, for which we found a high sensitivity in this study. Other assumptions that were investigated had only small effects on the forcing. For the reference run we find a minimum in the aerosol forcing of approximately −5 W m^-2 near the most polluted areas in Europe, and a maximum of approximately 2 W m^-2 over North Africa. A warming effect is also found for the Arctic region, with forcing values up to 0.4 W m^-2.     

The modality of particle size distributions of environmental aerosols

Knowledge of the distribution of airborne particulate matter into size fractions has become an increasing area of focus when examining the effects of air pollution. While total number and mass concentrations may play an important role in exposure and risk assessment analyses, often an understanding of the particle size distributions provides more information on the type of atmospheric processes resulting in the distributions. The modality of the particle size distribution is one such aspect that has been associated with the aerosol formation mechanisms. The aim of this work is to provide a detailed analysis of the modal characteristics of a large number of particle size spectra collected over a period of three years for a range of ambient aerosol types. Measurements of over 6000 size distributions in the size range 0.016–30 μm were made using a scanning mobility particle sizer and an aerodynamic particle sizer for various ambient aerosols including: traffic influenced, urban, vegetation burning influenced, marine, modified background and suburban. Advanced data analytical procedures were adopted to combine the distributions from the two instruments for the calculation of the volume size distributions to allow clear interpretation of the modal characteristics. It was determined that, while in most cases there is a distinct nuclei mode in the number size distribution, this does not translate to a nuclei mode in the volume size distribution. Furthermore, while many of the number size distributions were different for each aerosol studied, the volume distributions were similar. This finding has serious implications for the setting of mass-based air quality standards.     

Size Distribution of Participates Emitted from a Horizontal Spike Soderberg Aluminum Reduction Cell

Aerosol size distributions were measured in the air exhausted from a horizontal spike Soderberg aluminum reduction cell at the Kaiser Aluminum and Chemical Corporation plant in Tacoma, Wash. The particle size distributions were measured with the University of Washington cascade impactor, developed specifically for source testing. The particle mass concentrations and size distributions were found to vary significantly with changes in the cell process operations. For a typical aerosol size distribution at the exit of the cell hood the mass mean particle diameter was 5.5 microns and the particle size standard geometric deviation was 25.     

Chemical species’ contributions to the upper extremes of aerosol fine mass

Frequency distributions of the major chemical components of aerosol fine mass are shown to illustrate the respective species’ contributions to the range of observed fine particle mass concentration. The magnitude of a species’ contribution to the upper extremes of aerosol fine mass is relevant to control scenarios that seek to improve worst day fine particle conditions, or in many cases worst day visibility. We summarize the relative contributions of fine particle sulfate, nitrate, carbon, and soil plus sea salt to the upper extremes of aerosol fine mass based on Interagency Monitoring of PROtected Visual Environments (IMPROVE) data collected at monitoring locations across the United States during 1995 through 1999. The data show that the spatial pattern of a given chemical species’ contribution to the upper extremes of aerosol fine mass is often quite different than at lower fine mass concentrations. In some cases, the monitoring data suggest a casual relationship between specific aerosol source regions and the magnitude in which a species’ contribution to the upper extremes of fine mass is elevated above the contribution to median fine mass concentrations.     

Variation of mass scattering efficiencies in IMPROVE

The Interagency Monitoring of Protected Visual Environments (IMPROVE) equation used to assess compliance under the U.S. Environmental Protection Agency (EPA) Haze Rule assumes that dry mass scattering efficiencies for aerosol chemical components are constant. However, examination of aerosol size distributions and chemical composition during the Big Bend Regional Aerosol and Visibility Observational Study and the Southeastern Aerosol and Visibility Study suggests that volume and mass scattering efficiencies vary directly with increasing particle light scattering and aerosol mass concentration. This is consistent with the observation that particle distributions were shifted to larger sizes under more polluted conditions and appears to be related to aging of the aerosol during transport to remote locations.     

Calculated Droplet Size Distributions and Opacities of Condensed Sulfuric Acid Aerosols

The properties of condensed polydisperse sulfuric acid aerosols in industrial flue gas were calculated. The condensed aqueous acid volume concentration, composition, droplet size distributions and condensed plume opacity were calculated for typical flue gas compositions, condensation nucleus size distributions and flue gas dilution ratios. The assumed initial flue gas at 170°C contained 0.035 g/acm fly ash particles, 1-20% water vapor, and 1-50 ppmv sulfuric acid vapor. The assumed gas cooling mechanism was by adiabatlc dilution with cool ambient air. Polydisperse droplet growth was calculated by assuming equal surface area increase for each particle. The calculations show that sulfuric acid condensation should have minimal effect on particles larger than 1 μm, but will form a high concentration of particles in the narrow size range of 0.05-0.5 μm diameter. Depending on the initial sulfuric acid and water vapor concentrations in the hot flue gas, the calculated maximum plume opacity following gas dilution ranged from 5% to 25%, compared to 4% for the dry condensation nucleus aerosol.     

Growth of ultrafine particles by brownian coagulation

Current atmospheric observations tend to support the view that continental tropospheric aerosols (particularly urban aerosols) show multimodal mass distributions in the size range of 0.01–100 μm. The origin of these aerosols is both natural and anthropogenic. Recently, trimodal sub-μm size distributions from combustion measurements at 0.008, 0.035 and 0.15 μm were also observed. Our interest in the present study is the secondary process of growth of sub-μm size aerosols by the coagulation process alone. Using the ‘J-space’ (integer-space) distribution method of Salk (Suck) and Brock (1979, J. Aerosol Sci.10, 58–590), we report an accurate numerical simulation study of the evolution of ultrafine to fine particle size distributions. Comparision with the analytic solution of Scott (1968, J. atmos. Sci.25, 54–64) was made to test the accuracy of our J-space or integer-space distribution method. Our multimodal sub-μ particle size distribution study encompassed the particle size range of 0.001–0.20 μm. Details of particle growth in each mode and interaction between different modes in the multimodal distribution were qualitatively analyzed.     

Variation of Mass Scattering Efficiencies in IMPROVE

Abstract

The Interagency Monitoring of Protected Visual Environments (IMPROVE) equation used to assess compliance under the U.S. Environmental Protection Agency (EPA) Haze Rule assumes that dry mass scattering efficiencies for aerosol chemical components are constant. However, examination of aerosol size distributions and chemical composition during the Big Bend Regional Aerosol and Visibility Observational Study and the Southeastern Aerosol and Visibility Study suggests that volume and mass scattering efficiencies vary directly with increasing particle light scattering and aerosol mass concentration. This is consistent with the observation that particle distributions were shifted to larger sizes under more polluted conditions and appears to be related to aging of the aerosol during transport to remote locations.     

Characterisation of single particles from in-port ship emissions

Emissions from shipping traffic may impact severely upon air quality in port cities. In this study, the size and composition of freshly emitted individual ship exhaust particles has been investigated using an aerosol time-of-flight mass spectrometer (ATOFMS) co-located with a suite of real-time instrumentation at a site in the Port of Cork, Ireland. The collected spectra were clustered using the K-means algorithm and a unique ship exhaust class containing internally mixed elemental and organic carbon, sodium, calcium, iron, vanadium, nickel and sulfate was identified. Over twenty sharp emission events were observed for this particle type during the three week measurement period in August 2008. Coincident increases in mass concentrations of sulfate, elemental carbon and particles below 2.5 μm in diameter (PM_2.5) were also observed during these events. Simultaneous scanning mobility particle sizer (SMPS) measurements indicate that the vast majority of freshly emitted ship exhaust particles lie in the ultrafine mode (<100 nm diameter). A second particle class consisted of internally mixed organic carbon, elemental carbon, ammonium and sulfate, and is tentatively attributed to aged or regionally transported ship exhaust. The results suggest that ATOFMS single particle mass spectra, when used in conjunction with other air quality monitoring instrumentation, may be useful in determining the contribution of local shipping traffic to air quality in port cities.     

Simulation of the evolution of particle size distributions in a vehicle exhaust plume with unconfined dilution by ambient air

Over the past several years, numerous studies have linked ambient concentrations of particulate matter (PM) to adverse health effects, and more recent studies have identified PM size and surface area as important factors in determining the health effects of PM. This study contributes to a better understanding of the evolution of particle size distributions in exhaust plumes with unconfined dilution by ambient air. It combines computational fluid dynamics (CFD) with an aerosol dynamics model to examine the effects of different streamlines in an exhaust plume, ambient particle size distributions, and vehicle and wind speed on the particle size distribution in an exhaust plume. CFD was used to calculate the flow field and gas mixing for unconfined dilution of a vehicle exhaust plume, and the calculated dilution ratios were then used as input to the aerosol dynamics simulation. The results of the study show that vehicle speed affected the particle size distribution of an exhaust plume because increasing vehicle speed caused more rapid dilution and inhibited coagulation. Ambient particle size distributions had an effect on the smaller sized particles (approximately 10 nm range under some conditions) and larger sized particles (>2 microm) of the particle size distribution. The ambient air particle size distribution affects the larger sizes of the exhaust plume because vehicle exhaust typically contains few particles larger than 2 microm. Finally, the location of a streamline in the exhaust plume had little effect on the particle size distribution; the particle size distribution along any streamline at a distance x differed by less than 5% from the particle size distributions along any other streamline at distance x.     

Size Distribution and Sources of Aerosol in Launceston,Australia, during Winter 1997

ABSTRACT

As part of a pilot study into the chemical and physical properties of Australian fine particles, a suite of aerosol samples was collected at Ti Tree Bend in Launceston, Tasmania, during June and July 1997. This period represents midwinter in the Southern Hemisphere, a period when aerosol sources in Launceston are dominated by smoke from domestic wood burning. This paper describes the results from this measurement campaign, with the aim of assessing the effect of wood smoke on the chemical and physical characteristics of ambient aerosol. A micro orifice uniform deposit impactor (MOUDI) was used to measure the size distributions of the aerosol from 0.05 to 20 n m aerodynamic diameter. Continuous measurements of fine particle mass were made using a PM_2.5 tapered element oscillating microbalance (TEOM) and light scattering coefficients at 530 nm were measured with nephelometers.

Mass size distributions tended to be bimodal, with the diameter of the dominant mode tending to smaller sizes with increases in total mass. Non-sea salt potassium and polycyclic aromatic hydrocarbons (PAHs) were used as chemical tracers for wood smoke. Wood smoke was found to increase absolute particle mass (enough to regularly exceed air quality standards), and to concentrate mass in a single mode below 1 μm aerodynamic diameter. The acid-base equilibrium of the aerosol was altered by the wood smoke source, with free acidity hydrogen ion, non-sea salt sulfate, and ammonium concentrations being higher and the concentration of all species, including nitrate (to differing extents), focused in the fine particle size ranges. The wood smoke source also heavily influenced the aerosol scattering efficiency, adding to a strong diurnal cycle in both mass concentration and light scattering.