Estimates of Particle Hygroscopicity during the Southeastern Aerosol and Visibility Study

ABSTRACT

Aerosol water content was determined from relative humidity controlled optical particle counter (ASASP-X) size distribution measurements made during the Southeastern Aerosol and Visibility Study (SEAVS) in the Great Smoky Mountains National Park during summer 1995. Since the scattering response function of the ASASP-X is sensitive to particle refractive index, a technique for calibrating the ASASP-X for any real refractive index was developed. A new iterative process was employed to calculate water mass concentration and wet refractive index as functions of relative humidity. Experimental water mass concentrations were compared to theoretically predicted values assuming only ammonium sulfate compounds were hygroscopic. These comparisons agreed within experimental uncertainty. Estimates of particle hygroscopicity using a rural aerosol model of refractive index as a function of relative humidity demonstrated no significant differences from those made with daily varying refractive index estimates. Although aerosol size parameters were affected by the assumed chemical composition, forming ratios of these parameters nearly canceled these effects.     

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.     

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.     

Hygroscopic organic aerosols during BRAVO?

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.     

Hygroscopic Organic Aerosols during BRAVO?

Abstract

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 µm (PM_2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM_2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.     

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%.     

Characterization of particulate matter concentrations during controlled indoor activities

Indoor sources have been identified as a major contributor to the increase of particle concentration in indoor environments. The work presented here is a study of the characteristics of particulate matter number size distribution and mass concentration under controlled indoor activities in a laboratory room. The objective is to characterize particulate matter concentrations indoors resulted under the influence of specific sources. Measurements were performed in an empty laboratory (period September–October 2006) using a GRIMM SMPS+C system (particle size range between 11.1 and 1083.3 nm), a DustTrak Aerosol Monitor (TSI) and a P-Trak Ultrafine Particle Counter (TSI). The studied indoor activities included candle burning, hot plate heating, water boiling, onion frying, vacuuming, hair drying, hair spraying, smoking and burning of incense stick. The AMANpsd computer algorithm was used to evaluate the modal structure of measured particle number size distribution data. Furthermore, the change of the particle number size distribution shape under the influence of different emission sources was studied versus time. Finally the particle emission rates were computed. High particle number concentrations were observed during smoking, onion frying, candle burning and incense stick burning. The highest particle mass concentrations were measured during smoking and hair spraying. The shift of the particle size distribution to larger diameters suggests the presence of strong coagulation effect during candle burning, incense stick burning, smoking and onion frying. The size distribution was mainly bimodal during onion frying and candle burning, whereas the size distribution remained unimodal during incense stick burning and smoking experiments.     

Contamination from electrically conductive silicone tubing during aerosol chemical analysis

Electrically conductive silicone tubing is used to minimize losses in sampling lines during the analysis of airborne particle size distributions and number concentrations. We report contamination from this tubing using gas chromatography–mass spectrometry (GC–MS) of filter-collected samples as well as by particle mass spectrometry. Comparison of electrically conductive silicone and stainless steel tubing showed elevated siloxanes only for the silicone tubing. The extent of contamination increased with length of tubing to which the sample was exposed, and decreased with increasing relative humidity.     

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

ABSTRACT

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 μm inlet. Fine particle (<2.5 μm) 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.     

The effect of aerosol optical depth on rainfall with reference to meteorology over metro cities in India

Rainfall is a key link in the global water cycle and a proxy for changing climate; therefore, proper assessment of the urban environment’s impact on rainfall will be increasingly important in ongoing climate diagnostics and prediction. Aerosol optical depth (AOD) measurements on the monsoon seasons of the years 2008 to 2010 were made over four metro regional hotspots in India. The highest average of AOD was in the months of June and July for the four cities during 3 years and lowest was in September. Comparing the four regions, Kolkata was in the peak of aerosol contamination and Chennai was in least. Pearson correlation was made between AOD with climatic parameters. Some changes in the parameters were found during drought year. Temperature, cloud parameters, and humidity play an important role for the drought conditions. The role of aerosols, meteorological parameters, and their impacts towards the precipitation during the monsoon was studied.     

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.     

Continuous measurements of aerosol physical properties in the urban atmosphere

Simultaneous continuous measurements have been made at an urban background site of PM₁₀ mass by Tapered Element Oscillating Microbalance, particle number density by condensation nucleus counter and Fuchs surface area using an epiphaniometer. Concurrent measurements of gaseous NO_x and CO have been used to indicate road traffic emissions, and data from a nearby meteorological station have been used for relative humidity, temperature and windspeed. The data indicate that particle number density is a far better indicator of traffic activity than PM₁₀ mass which is strongly influenced by a high background, and also tends to peak rather later than the gaseous pollutants and particle number, presumably as a result of advection of accumulation mode aerosol. PM₁₀ mass and Fuchs surface area generally show a very similar temporal trend, although there is a tendency for the ratio of surface area to dry particle mass to increase with relative humidity. The sampling period included bonfire night celebrations which caused substantial increases in all particle parameters, although the ratio of particle mass to number was considerably higher than for the morning rush hour road traffic-influenced peak.     

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.     

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.     

An inexpensive dual-chamber particle monitor: laboratory characterization

In developing countries, high levels of particle pollution from the use of coal and biomass fuels for household cooking and heating are a major cause of ill health and premature mortality. The cost and complexity of existing monitoring equipment, combined with the need to sample many locations, make routine quantification of household particle pollution levels difficult. Recent advances in technology, however, have enabled the development of a small, portable, data-logging particle monitor modified from commercial smoke alarm technology that can meet the needs of surveys in the developing world at reasonable cost. Laboratory comparisons of a prototype particle monitor developed at the University of California at Berkeley (UCB) with gravimetric filters, a tapered element oscillating microbalance, and a TSI DustTrak to quantify the UCB particle monitor response as a function of both concentration and particle size and to examine sensor response in relation to changes in temperature, relative humidity, and elevation are presented here. UCB particle monitors showed good linearity in response to different concentrations of laboratory-generated oleic acid aerosols with a coarse (mass median diameter, 2.1 microm) and fine (mass median diameter, 0.27-0.42 microm) size distributions (average r2 = 0.997 +/- 0.005). The photoelectric and ionization chamber showed a wide range of responses based on particle size and, thus, require calibration with the aerosol of interest. The ionization chamber was five times more sensitive to fine rather than coarse particles, whereas the photoelectric chamber was five times more sensitive to coarse than fine. The ratio of the response between the two sensors has the potential for mass calibration of individual data points based on estimated parameters of the size distribution. The results demonstrate the significant potential of this monitor, which will facilitate the evaluation of interventions (improved fuels, stoves, and ventilation) on indoor air pollution levels and research on the impacts of indoor particle levels on health in developing countries.     

Regional differences of column-related aerosol parameters in Germany

With the development of satellite experiments supplementary and validating ground-based measurements are gaining growing importance for the inference and evaluation of radiation-related aerosol parameters. Both kinds of measurements have been conducted and interpreted mainly under globally or locally restricted aspects for a limited time period only. Results are presented from four rural regions (coastal zone, lowlands, highlands, high mountain); they are column-related aerosol parameters, deduced from monitoring programs of spectral aerosol optical depth (AOD) as well as almucantar sky irradiance measurements. After 13 years of continuous measurements of trends and variations in aerosol optical depths, these results are based on 5 years of data collection (1994–1998). There are significant differences among the parameters of the four regions when related to the inversion method of the AOD spectra. A clear interdependence was found between all column-related parameters and the real part of the refractive index, which in turn depends on the chosen retrieval method. The differences among the four regions are characterized mainly by their different altitudes, with relative humidity being responsible for their internal variation. An increase in the relative humidity from 35 to 55–60% influences the most interesting parameters such as refractive index (real part), hemispheric backscattered fraction b, and direct radiative forcing ΔF as follows: The real part of the refractive index decreases from 1.6±0.05 to 1.42±0.04, b decreases by 8–10%, and, due to the increase in AOD, ΔF increases by about 20% in the spectral region 0.4–1.0 μm. The quantities of the parameters depend on the retrieval methods too.     

Evolution of vehicle exhaust particles in the atmosphere

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.     

Aerosol composition as a function of haze and humidity levels in the Southwestern U.S.

The observed composition of visibility-reducing aerosols in the Grand Canyon region is summarized in climatological terms. Observations are from SCENES, a measurement program extending from 1984 to 1989. Results are presented as average mass balances stratified by various factors.Aerosols were found to exhibit substantial seasonal variation, but little systematic diurnal variation. Crustal material was a dynamic component, and peaked during springtime. Aerosol composition, but not total concentration, depended strongly on ambient relative humidity, with crustal material augmented at low humidities and sulfates augmented at high humidities. Total fine-particle concentrations correlated strongly with light scattering, as expected; however, little association between chemical composition and light scattering was observed.     

Determination of aerosol yields from 3-methylcatechol and 4-methylcatechol ozonolysis in a simulation chamber

Secondary Organic Aerosol (SOA) formation during the ozonolysis of 3-methylcatechol (3-methyl-1,2-dihydroxybenzene) and 4-methylcatechol (3-methyl-1,2-dihydroxybenzene) was investigated using a simulation chamber (8 m³) at atmospheric pressure, room temperature (294 ± 2 K) and low relative humidity (5–10%). The initial mixing ratios were as follows (in ppb): 3-methylcatechol (194–1059), 4-methylcatechol (204–1188) and ozone (93–531). The ozone and methylcatechol concentrations were followed by UV photometry and GC–FID (Gas chromatography–Flame ionization detector), respectively and the aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted methylcatechol concentrations assuming a particle density of 1.4 g cm^?3. The aerosol formation yield increases as the initial methylcatechol concentration increases, and leads to aerosol yields ranging from 32% to 67% and from 30% to 64% for 3-methylcatechol and 4-methylcatechol, respectively. Y is a strong function of M_o and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. These data are comparable to those published in a recent study on secondary organic aerosol formation from catechol ozonolysis. To our knowledge, this work represents the first investigation of SOA formation from the ozone reaction with methylcatechols.     

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.