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.     

Nucleation of sulfuric acid-water and methanesulfonic acid-water solution particles: Implications for the atmospheric chemistry of organosulfur species

Binary nucleation theory is applied to the formation of aqueous sulfuric acid and aqueous methanesulfonic acid particles and the relative rates of aerosol formation in humid atmospheres are compared. An integral model is presented which describes nucleation of solution particles, aerosol growth, and condensable vapor source and depletion rates. To extend this model, the water activities of the ternary solution, sulfuric acid-methanesulfonic acid-water, are estimated, and growth of the nucleated aerosol by incorporation of both types of acid is considered. Predictions of both forms of the model are compared with the experimental results of Hatakeyama et al. [Atmospheric Environment19, 135–141 (1985)] for the photooxidation of dimethylsulfide in humid air.     

Tropospheric sulfate aerosol formation via ion-ion recombination

We propose a source of aerosols in the lower atmosphere associated with the creation, growth, and recombination of ubiquitous cosmogenically generated ions. This particle source should be favorable in the relatively clean, stable marine boundary layer, providing a uniform, continuous fine particle generator in the presence of dimethylsulfide emissions. Through this mechanism, new sulfate aerosols can be formed at sulfuric acid vapor partial pressures well below the supersaturations required for homogeneous binary nucleation of sulfuric acid/water solutions, which is consistent with numerous observations of new particle formation under sub-saturated conditions. The evolving aerosols in turn control the acid vapor concentration and thus modulate the sizes of the precursor ions and the rate of new particle formation. A simple model representing this nonlinear coupled system predicts that the physical and chemical processes connecting ions, vapors, and aerosols effectively constrain the particle population to a relatively narrow range of values. This self-limiting behavior may explain in part the apparent stability of the marine sulfate aerosol, with mean concentrations of the order of several hundred per cubic centimeter.     

Comparison of real-time instruments used to monitor airborne particulate matter

Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakersfield, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 microns (PM2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of approximately 3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH4NO3 observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.     

Comparison of ambient particle surface area measurement by epiphaniometer and SMPS/APS

During measurement campaigns at an urban background and a rural site, simultaneous measurements of particle size distributions using a scanning mobility particle sizer (SMPS)/aerodynamic particle sizer (APS) combination and Fuchs surface using an epiphaniometer have been made. The epiphaniometer was calibrated using sub-100 nm monodisperse aerosol and it was found that a calibration based upon particle electrical mobility diameters measured with a SMPS was consistent irrespective of the use of singlet particles of sodium chloride and ammonium sulphate or clusters of carbon. The field intercomparison of surface areas derived directly from the epiphaniometer and calculated from the size distributions determined by the SMPS/APS combination showed a good agreement of Fuchs surface estimates at both measurement sites. However, attempts to estimate a “geometric” surface area from the epiphaniometer data led to significant divergence from the estimates of the SMPS/APS combination when there was a significant fraction of coarser (>700 nm) particles contributing to the aerosol surface area.     

Tropospheric Sulfate Aerosol Formation Via Ion-Ion Recombination

ABSTRACT

We propose a source of aerosols in the lower atmosphere associated with the creation, growth, and recombination of ubiquitous cosmogenically generated ions. This particle source should be favorable in the relatively clean, stable marine boundary layer, providing a uniform, continuous fine particle generator in the presence of dimethylsulfide emissions. Through this mechanism, new sulfate aerosols can be formed at sulfuric acid vapor partial pressures well below the supersaturations required for homogeneous binary nucleation of sulfuric acid/water solutions, which is consistent with numerous observations of new particle formation under sub-saturated conditions. The evolving aerosols in turn control the acid vapor concentration and thus modulate the sizes of the precursor ions and the rate of new particle formation. A simple model representing this nonlinear coupled system predicts that the physical and chemical processes connecting ions, vapors, and aerosols effectively constrain the particle population to a relatively narrow range of values. This self-limiting behavior may explain in part the apparent stability of the marine sulfate aerosol, with mean concentrations of the order of several hundred per cubic centimeter.     

Comparison of measurement methods for the characterization of the black carbon emissions from a T63 turboshaft engine burning conventional and Fischer-Tropsch fuels

Emission measurements of black carbon (BC) mass were conducted on a T63 turboshaft engine, operated at idle and cruise power with conventional and alternative fuels, using an Artium LII-300 laser-induced incandescence analyzer (LII) and AVL model 483 micro soot sensor (MSS) photoacoustic instrument using the manufacturer’s calibration for both instruments. These measurements were compared with elemental carbon (EC) determined by manual and semicontinuous thermal-optical transmission analyses according to National Institute for Occupational Safety and Health (NIOSH) method 5040 as the reference method. The results indicate that both the LII and MSS instruments show good linear correlation with EC for the two fuels and two engine power conditions evaluated. The LII measurements were observed to be biased high (27–49%) and the MSS measurements were biased low (24–35%) relative to EC. The agreement between the instruments and the reference method was substantially improved by applying a calibration of the instruments against a common BC aerosol source. Test data also suggest that the two instruments show some sensitivity to particle size (or properties related to size), specifically for particles with a geometric mean diameter (GMD) <30 nm. This sensitivity is problematic, since new engines or certain combustion conditions in current engines will produce smaller particles compared with the T63 model tested in this study. Further assessments of instrument performance for particles within this size range are therefore warranted.

Implications: Accurate black carbon emission measurements are needed to certify new and in-production commercial aircraft engines. Both the Artium LII-300 and AVL 483 micro soot sensor are currently approved by the International Civil Aviation Organization for this purpose. This study compares the two instruments against elemental carbon (EC) using NIOSH method 5040 as the reference using a T63 turboshaft engine. The results indicate that both instruments correlate reasonably well with EC, and the correlation substantially improved when applying a calibration against a common aerosol source. Sensitivity to particle size may be an issue for both instruments.     

A Portable Electrical Analyzer for Size Distribution Measurement of Submicron Aerosols

An electrical aerosol analyzer capable of performing rapid, in situ size distribution measurement on aerosols from 0.003 to 1 μm diameter has been described. The instrument is based on the “diffusion charging-mobility analysis” principle first described by Whitby and Clark. The prototype instrument has a total volume of 3.75 ft³ and a total weight of 60 lb, and is sufficiently portable to be used on small airplanes and ground based vehicles for mobile air pollution studies. The paper describes the design, operation, and performance of the instrument. Sample data are presented showing the size distributions of aerosols measured by the instrument on board a small research aircraft over the Los Angeles basin at several different altitudes. In addition, data are presented showing the size distribution of smog chamber aerosols and aerosols produced by a conventional Collison atomizer.     

Removal characteristics of sulfuric acid aerosols from coal-fired power plants

With increasing attention on sulfuric acid emission, investigations on the removal characteristics of sulfuric acid aerosols by the limestone gypsum wet flue gas desulfurization (WFGD) system and the wet electrostatic precipitator (WESP) were carried out in two coal-fired power plants, and the effects of the WFGD scrubber type and the flue gas characteristics were discussed. The results showed that it was necessary to install the WESP device after desulfurization, as the WFGD system was inefficient to remove sulfuric acid aerosols from the flue gas. The removal efficiency of sulfuric acid aerosols in the WFGD system with double scrubbers ranged from 50% to 65%, which was higher than that with a single scrubber, ranging from 30% to 40%. Furthermore, the removal efficiency of WESP on the sulfuric acid aerosols was from 47.9% to 52.4%. With increased concentrations of SO₃ and particles in the flue gas, the removal efficiencies of the WFGD and the WESP on the sulfuric acid aerosols were increased.

Implications: Investigations on removal of sulfuric acid aerosols by the WFGD and the WESP in the power plants were aimed at the control of sulfuric acid emission. The results showed that the improvement of the WFGD system was beneficial for the reduction of sulfuric acid emission, while the WESP system was essential to control the final sulfuric acid aerosol concentration.     

Electrical Measurement of the Mass Concentration of a Self-Preserving Aerosol Size Distribution

Recently fifty-eight measurements of urban aerosol size distributions by Clark have shown that these distributions agree quite well with the self preserving form proposed by Friedlander within the size range of 0.05 to 5 microns radius. This paper shows that for an aerosol obeying the self preserving distribution model, the volume concentration (and, hence, the mass concentration for constant density) is directly proportional to the electric current collected when the aerosol is unipolarly charged, passed through a weak electric field to remove particles smaller than 0.05 micron and then collected by a current collector. It is shown that the linear relation between the mass concentration and collected current is independent of the unipolar charging method used. A test of this theory using Clark’s electric counter data was encouraging and suggests that the electric measurement of urban aerosol mass concentrations by properly designed instruments may be feasible.     

Studies on Sulfuric Acid Mist Downwind from a Sulfuric Acid Manufacturing Plant

Air pollution downstream from a sulfuric acid manufacturing plant is comprised of two aspects, the amount of acid mist fallout and the concentration in the atmosphere. This investigation shows that it is desirable to determine each of these by an independent method of collection. Pans of distilled water were used to collect and determine the sulfuric acid mist fallout and an electrostatic precipitator was used to determine the sulfuric acid mist concentration in the atmosphere. The use of Stokes’ Law to convert the results obtained by one method to those obtained by the other requires a knowledge of the particle size of the sulfuric acid mist droplets. Data presented show that tho uso of an average particle size can yield a picture of pollution which is in error by many orders of magnitude. The study shows that areas adjacent to a plant may be subjected to fallout of rather large particle size when there are not adequate methods for removal from the emission or byproduct gases.     

Investigation of the positive artifact formation during sampling semi-volatile aerosol using wet denuders

Wet denuders are used in several steam-based semi-continuous aerosol monitors to avoid gaseous absorption artifacts and pre-humidify the air stream, while simultaneously allowing measurements of water-soluble gaseous species. Unlike dry denuders, wet denuders saturate the sample air stream with water vapor, which can lead to re-partitioning of water-soluble volatile species to the aerosol phase, thereby causing a positive artifact in aerosol measurements. This paper investigates the magnitude of the positive artifact formation occurring in wet denuders using modeling techniques. Gaseous nitric acid was used as an example of volatile water-soluble gas in both flat and annular wet denuders. We have also verified the occurrence of the positive artifact in a flat wet denuder through a laboratory experiment. The model results indicate that the magnitude of the artifact is rather limited under typical conditions being less than 2.5% of ambient nitric acid concentration for the flat denuder and less than 0.6% for the annular denuder. The magnitude of the artifact increases with condensational sink of the aerosol (i.e. with the mean aerosol size and number concentration) and aerosol water solubility. While the artifact is relatively small in the absolute sense, it could be substantial for aerosol nitrate measurements, especially in ammonia limited conditions, when the concentration of the nitric acid is high and the concentration of nitrate is low. Therefore, we recommend that the artifact is assessed regularly by replacing the wet denuder with a dry denuder.     

Aerosol maps from GOME data

In this paper, we present a methodology to calibrate the surface reflectance seen by satellite and validate the aerosol optical properties retrieved by the GOME instrument. Data are also visualized in maps by a tool properly developed, named GOMEView. The validation procedure is based on ground measurements obtained by sunphotometers. Results show that calibration of the surface reflectance is crucial to obtain the best results, i.e. in agreement with the ground measurements. Aerosol data have also been classified on the basis of their optical properties evidencing for instance, the presence of desert aerosol over the sea along the west coast of Sahara. Cloud retrievals were also analyzed in terms of their occurrence and amount.     

Respiratory Responses of Exercising Asthmatic Volunteers Exposed to Sulfuric Acid Aerosol

Young asthmatic adult volunteers (N = 27) were exposed in an environmental chamber to sulfuric acid aerosol at concentrations near 0, 122, 242, and 410 μg/m³, in purified background air at 22° C and 50 percent relative humidity. The polydisperse aerosol had a mass median aerodynamic diameter near 0.6 μm. Exposures occurred in random order at one-week intervals. Each lasted 1 h, during which subjects exercised (mean ventilation 42 L/min) and rested during alternate 10-min periods. Specific airway resistance and forced expiratory function were measured pre-exposure, after the initial exercise, and at end-exposure. Bronchial reactivity was determined by challenge with cold air immediately post-exposure. Symptoms were monitored during exposure for one week afterward. Exercise-induced bronchospasm was observed under all conditions. Physiologic and symptom changes possibly attributable to sulfuric acid exposure were small and not statistically significant. Our largely negative results contrast with positive findings elsewhere at lower acid doses. Possible explanations include different clinical characteristics of subjects and different routes of breathing.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

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.     

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 Portable,Battery-Operated,Immediate-Readout Dust-Particle Analyzer

A portable, battery-operated, electro-optical dust analyzer operating on the principle of light scattering from individual dust particles in air drawn through a high-intensity light field has been developed for monitoring dust levels where external power may be unavailable. The instrument counts and size-discriminates airborne particles over two size ranges upwards of 0.3 microns with immediate readout. A dilution mechanism permits analysis of particulate concentrations as high as 2400 particles/cm³ on each channel. The self-contained Ni-Cd batteries are rechargeable. Total weight, including batteries and all components, is approximately 14 Ib. Total power used, mainly for pumping a filtered air sheath at 300 cm/sec and for the light source, is less than 34 watts. Another unique feature is the flow system designed for turbulence suppression.

Electronic calibration in terms of number of particles/cm³ for each size range is accomplished in the laboratory by means of a pulse generator with respect to which the readout indicator is calibrated for count. The input voltages to the pulse-height discriminators are appropriately attenuated for various pulse amplitudes simulating the output of the light-sensitive pickup, a photomultiplier tube.Pulse height as a function of particle size was measured for polystyrene latex beads ranging from 0.3 to 2 microns in diameter. Good correlation is obtained with results from commercial analyzers.

Field surveys have been undertaken with the CAES prototype analyzer at various sites in central Pennsylvania and at numerous sampling points within the cities of Pittsburgh and Philadelphia. Particulate concentrations as high as 1400 particles/ cm³ have been measured at a coal cleaning plant.     

Design and Calibration of A High Volume Cascade Impactor

The purpose of this study was to develop an air sampling device capable of classifying large quantities of airborne particulate matter into discrete size fractions. Such frac-tionation will facilitate chemical analysis of the various particulate pollutants and thereby provide a more realistic assessment of the effects of particulate matter on human beings.

A 30 cfm, 5 stage cascade impactor of the slit-type has been constructed and calibrated. The calibration aerosol consisted of six different sizes of monodispersed methylene blue produced with a spinning disc generator. The test aerosol sizes varied from 1.35 to 14 μm. The calibration was challenged with heterodispersed aerosols of methylene blue, Arizona road dust, and DOP.     

Size distribution and sources of aerosol in Launceston, Australia, during winter 1997

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 microns aerodynamic diameter. Continuous measurements of fine particle mass were made using a PM2.5 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 micron 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.