Modelling the formation and atmospheric transport of secondary inorganic aerosols with special attention to regions with high ammonia emissions

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m^?3 whereas the ammonium sulfate concentrations are about 5 μg m^?3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m^?3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH₃ emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH₃ emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.     

Optical properties of the San Joaquin Valley aerosol collected during the 1995 integrated monitoring study

Optical, filter chemistry, and cascade impactor data collected during the winter intensive of the IMS95 Study in the San Joaquin Valley (SJV) of California were analyzed to determine the light-extinction efficiency of aerosol species. Regression of light scattering by particles (b_sp) measured by a heated nephelometer without a size selective inlet against PM_2.5 front filter mass gave a scattering efficiency of 3.67±0.05 m²/g with an R² (fraction of variance explained) of 0.94. Division of the aerosol into two components and applying two different corrections to the filter data for nitrate and organic carbon on the backup filter gave scattering efficiencies of 3.7±0.3 or 4.1±0.2 m²/g for the salts composed of sulfate, nitrate, and ammonium and 2.9±0.2 or 3.1±0.2 m²/g for all other species with R² of 0.985 and 0.986. The ambient b_sp measured by an open nephelometer was a simple function of PM_2.5 mass and relative humidity (RH), giving R² of 0.90 and 0.88 for two different RH sensors. Variations in PM_2.5 size distribution and composition did not have an important effect on ambient b_sp. The RH data from each sensor were repeatable enough to show the existence of a simple dependence of aerosol water uptake on RH, but RH sensor calibration uncertainties prevented determining this dependence. Inversion of MOUDI cascade impactor data gave sulfate and nitrate mass median diameters (MMD) between 0.4 and 0.8 μm. Mie scattering calculations based on MOUDI data provided humidity-dependent extinction efficiencies for the principal aerosol chemical species. These efficiencies combined with particle filter data showed that ammonium nitrate was the dominant contributor to wintertime light extinction. Source apportionment showed that light extinction was dominated by emissions sources contributing to the formation of secondary species, especially nitrate. These wintertime data are not expected to apply to summertime in the SJV.     

Fine particulate (PM2.5) composition in Atlanta, USA: assessment of the particle concentrator-Brigham Young University organic sampling system, PC-BOSS, during the EPA supersite study

Aerosol concentrations of carbonaceous material, sulfate, and nitrate for samples obtained using a newly designed PC-BOSS are reported. The results indicated that PM_2.5 composition in Atlanta was dominated by sulfate and organic material, with low concentrations of particulate nitrate. Observed average particulate component concentrations for the 26-day study period were: sulfate, 12.2 μg/m³ (17.0 μg/m³ as ammonium sulfate); non-volatile organic material, 11.4 μg OM/m³ (assumes organic material, OM, is 61% C); semi-volatile organic compounds (SVOC) lost from particles during sampling, 5.3 μg OM/m³; filter retained nitrate, 0.1 μg/m³ (0.2 μg/m³ as ammonium nitrate); nitrate lost from particles, 0.3 μg/m³ (0.4 μg/m³ as ammonium nitrate); and soot (elemental carbon), 1.5 μg/m³. The PC-BOSS particle concentrator efficiency was obtained by comparison of the PC-BOSS sulfate data with sulfate data obtained from the Federal Reference Method (FRM) sampler. A modification of the PC-BOSS design to allow independent determination of this parameter is recommended.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

Simulation of aerosol direct radiative forcing with RAMS-CMAQ in East Asia

The air quality modeling system RAMS-CMAQ is developed to assess aerosol direct radiative forcing by linking simulated meteorological parameters and aerosol mass concentration with the aerosol optical properties/radiative transfer module in this study. The module is capable of accounting for important factors that affect aerosol optical properties and radiative effect, such as incident wave length, aerosol size distribution, water uptake, and internal mixture. Subsequently, the modeling system is applied to simulate the temporal and spatial variations in mass burden, optical properties, and direct radiative forcing of diverse aerosols, including sulfate, nitrate, ammonium, black carbon, organic carbon, dust, and sea salt over East Asia throughout 2005. Model performance is fully evaluated using various observational data, including satellite monitoring of MODIS and surface measurements of EANET (Acid Deposition Monitoring Network), AERONET (Aerosol Robotic Network), and CSHNET (Chinese Sun Hazemeter Network). The correlation coefficients of the comparisons of daily average mass concentrations of sulfate, PM2.5, and PM10 between simulations and EANET measurements are 0.70, 0.61, and 0.64, respectively. It is also determined that the modeled aerosol optical depth (AOD) is in congruence with the observed results from the AERONET, the CSHNET, and the MODIS. The model results suggest that the high AOD values ranging from 0.8 to 1.2 are mainly distributed over the Sichuan Basin as well as over central and southeastern China, in East Asia. The aerosol direct radiative forcing patterns generally followed the AOD patterns. The strongest forcing effect ranging from −12 to −8 W m⁻² was mainly distributed over the Sichuan Basin and the eastern China’s coastal regions in the all-sky case at TOA, and the forcing effect ranging from −8 to −4 W m⁻² could be found over entire eastern China, Korea, Japan, East China Sea, and the sea areas of Japan     

Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

Relationship between Sulfate Aerosol and Visibility

A PM₁₀ monitoring network was established throughout the South Coast Air Basin (SOCAB) in the greater Los Angeles region during the calendar year 1986. Annual average PM₁₀ mass concentrations within the Los Angeles metropolitan area ranged from 47.0 µg m^-3 along the coast to 87.4 µg m^-3 at Rubldoux, the furthest inland monitoring station. Measurements made at San Nicolas Island suggest that regional background aerosol contributes between 28 to 44 percent of the PM₁₀ aerosol at monitoring sites In the SOCAB over the long term average. Five major aerosol components (carbonaceous material, NO^- ₃, SO⁼ ₄, NH⁺ ₄, and soil-related material) account for greater than 80 percent of the annual average PM₁₀ mass at all on-land monitoring stations. Peak 24-h average mass concentrations of nearly 300 µg m^-3 were observed at inland locations, with lower peak values (?130–150 µg m^-3) measured along the coast. Peak-day aerosol composition was characterized by increased NO^- ₃ Ion and associated ammonium ion levels, as compared to the annual average. There appears to be only a weak dependence of PM₁₀ mass concentration on season of the year. This lack of a pronounced seasonal dependence results from the complex and contradictory seasonal variations in the major chemical components (carbonaceous material, nitrate, sulfate, ammonium ion and crustal material). At most sites within the Los Angeles metropolitan area, PM₁₀ mass concentrations exceeded both the annual and 24-h average federal and state of California PM₁₀ regulatory standards.     

Regional climate forcing of aerosol estimated by a box model for a rural site in Central Europe during summer

In the present work, a box model is applied to estimate the direct climate forcing of aerosol particles for rural air in Central Europe during summertime. In the model, the input parameters reflect regional character: data from satellite observations and other surface measurements are used referring to the selected area, Hungary. In the calculation of direct climate forcing of aerosol particles satellite observations serve as the source of incoming solar radiation intensity data and cloudiness, while different aerosol parameters of the model (mass extinction coefficient, chemical composition, scale height, hygroscopic growth factor, etc.) are based on local measurements. Finally, surface albedo of the area studied was determined on the basis of vegetation cover and precipitation amount. As the summary of our calculations, in Central Europe direct climate forcing of ammonium sulfate is equal to –2.4 W m⁻². The climate forcing of total carbon is composed of two terms. The forcings due to scattering and absorption are –1.0 and +0.2 W m⁻², respectively. In spite of the fact that the mass concentrations of ammonium sulfate and total carbon are similar, their contribution to the aerosol direct forcing is different. We conclude that ammonium sulfate plays the major role in this process and organics have an additional impact.     

Measurement and Analysis of the Relationship between Ammonia,Acid Gases,and Fine Particles in Eastern North Carolina

Abstract

An annular denuder system, which consisted of a cyclone separator; two diffusion denuders coated with sodium carbonate and citric acid, respectively; and a filter pack consisting of Teflon and nylon filters in series, was used to measure acid gases, ammonia (NH₃), and fine particles in the atmosphere from April 1998 to March 1999 in eastern North Carolina (i.e., an NH₃?rich environment). The sodium carbonate denuders yielded average acid gas concentrations of 0.23 μg/m³ hydrochloric acid (standard deviation [SD] ± 0.2 μg/m³); 1.14 μg/m³ nitric acid (SD ± 0.81 μg/m³), and 1.61 μg/m³ sulfuric acid (SD ± 1.58 μg/m³). The citric acid denuders yielded an average concentration of 17.89 μg/m³ NH₃ (SD ± 15.03 μg/m³). The filters yielded average fine aerosol concentrations of 1.64 μg/m³ ammonium (NH₄ ⁺;SD ± 1.26 μg/m³); 0.26 μg/m³ chloride (SD ± 0.69 μg/m³), 1.92 μg/m³ nitrate (SD ± 1.09 μg/m³), and 3.18 μg/m³ sulfate (SO₄ ^2?; SD ± 3.12 μg/m³). From seasonal variation, the measured particulates (NH₄ ⁺,SO₄ ^2?, and nitrate) showed larger peak concentrations during summer, suggesting that the gas-to-particle conversion was efficient during summer. The aerosol fraction in this study area indicated the domination of ammonium sulfate particles because of the local abundance of NH₃, and the long-range transport of SO₄ ^2? based on back trajectory analysis. Relative humidity effects on gas-to-particle conversion processes were analyzed by particulate NH₄ ⁺ concentration originally formed from the neutralization processes with the secondary pollutants in the atmosphere.     

Comparisons of coarse-mode aerosol nitrate and ammonium at two polluted coastal sites

Direct atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters and can be enhanced by heterogeneous reactions between gaseous atmospheric nitrogen species and aerosol sea salt, which increase deposition rates. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland. Major-ion aerosol concentrations were determined and temporal patterns were interpreted with the use of air-mass back trajectories. Low levels of terrestrially derived material were seen during periods of clean, onshore flow, with respective concentration ranges for nitrate and ammonium of 0.47–220 and below detection limit to 340 nmol m⁻³. Corresponding levels of marine derived material during these periods were high, with sodium concentrations ranging from 39 to 1400 nmol m⁻³. Highest levels of terrestrially derived material were seen during polluted, offshore flow, where the air had passed recently over strong source regions of the UK and northern Europe, with concentration ranges of nitrate and ammonium of 5.6–790 and 9.7–1000 nmol m⁻³, respectively. During polluted flow ∼40–60% of the nitrate was found in the coarse mode (>1 μm diameter) and under clean marine conditions almost 100% conversion was seen. In addition, our data suggests strong evidence for dissolution/coagulation processes that also shift nitrate to the coarse mode. Furthermore, such processes are thought also to give rise to the size-shifting of aerosol ammonium, since significant coarse-mode fractions of this species (∼19–45%) were seen at both sites. A comparison of the relative importance of nitrate and ammonium in the overall dry deposition of inorganic fixed-nitrogen at each site indicates that at Weybourne the mass-weighted dry deposition velocity of the latter is around double that seen at Mace Head with its resultant contribution to the overall inorganic nitrogen dry flux exceeding that of nitrate.     

Monitoring Deposition of Nitrogen-Containing Compounds in a High-Elevation Forest Canopy

Measurements of airborne (gaseous and aerosol), cloud water, and precipitation concentrations of nitrogen compounds were made at Mt. Mitchell State Park (Mt. Gibbs, ~2006 m MSL), North Carolina, during May through September of 1988 and 1989, An annular denuder system was used to ascertain gaseous (nitric acid, nitrous acid, and ammonia) and particulate (nitrate and ammonium) nitrogen species, and a chemiluminescence nitrogen oxides analyzer was used to measure nitric oxide and nitrogen dioxide. Measurements of NO₃ ^? and NH₄ ⁺ ions in cloud and rain water samples were made during the same time period. Mean concentrations of gaseous nitric acid, nitrous acid, and ammonia were 1.14 μg/m³, 0.3 μg/m³, and 0.62 μg/m³ for 1988, and 1.40 μg/m³,0.3 μg/m³, and 1.47 μg/m³ for 1989, respectively. Fine particulate nitrate and ammonium ranged from 0.02 to 0.21 μg/m³ and 0.01 to 4.72 μg/m³ for 1988, and 0.1 to 0.78 μg/m³ and 0.24 to 2.32 μg/m³ for 1989, respectively. The fine aerosol fraction was dominated by ammonium sulfate particles. Mean concentrations of nitrate and ammonium ions in cloud water samples were 238 and 214 μmol/l in 1988, and 135 and 147 μmol/l in 1989, respectively. Similarly, the concentrations of NO₃ and NH₄ ⁺ in precipitation were 26.4 and 14.0 μmol/l in 1988, and 16.6 and 15.2 μmol/l in 1989, respectively. The mean total nitrogen deposition due to wet, dry, and cloud deposition processes was estimated as ~30 and ~40 kg N/ha/year (i.e., ~10 and ~13 kg N/ha/growing season) for 1988 and 1989. Based on an analytical analysis, deposition to the forest canopy due to cloud interception, precipitation, and dry deposition processes was found to contribute ~60, ~20, and ~20 percent, respectively, of the total nitrogen deposition.     

Fine Particulate Chemical Composition and Light Extinction at Meadview,AZ

Abstract

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was ±0.6 μg/m³ organic material, ±0.3 μg/m³ ammonium sulfate, and ±0.07 μg/m³ ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Atmospheric Aerosol Composition and Concentration as a Function of Particle Size and of Time

As a step toward better understanding the reactive Los Angeles air basin atmosphere, a study was undertaken at the University of California—Riverside Campus, to determine the composition and concentration of atmospheric particulate matter as a function of particle size and time. The study involved developing a method for obtaining size-classified, time-fractionated aerosol samples amenable to chemical and physical (including microscopic) analysis. During a 15-day period, samples were obtained over 4-hr periods and subsequently analyzed for nitrate, sulfate, iron, and lead. Concentration of six gaseous pollutantsj total aerosol light-scattering, and several meteorological measurements were simultaneously recorded and averaged over the 4-hr intervals. This data was presented graphically to show the diurnal variation in and relationship between gaseous, particulate, and meteorological measurements. A strong relationship between gaseous peroxyacetyl nitrate, particulate nitrate, and aerosol light-scattering was found. High concentrations of ammonium nitrate particles, mainly in the 0.5-2μ, diameter size range, were found in the atmospheric particulate samples collected on days of very high smog (very limited visibility).     

Particulate contributions to light extinction and local forcing at a rural Illinois site

The light extinction and direct forcing properties of the atmospheric aerosol were investigated for a midwestern rural site (Bondville, IL) using field measurements, a semi-empirical light extinction model, and a radiative transfer code. Model inputs were based on the site measurements of the physical and chemical characteristics of atmospheric aerosol during the spring, summer, fall and winter of 1994. The light scattering and extinction coefficients were calculated and apportioned using the elastic light scattering interactive efficiency (ELSIE) model (Sloane and Wolff, 1985, Atmospheric Environment 19(4), 669–680). The average efficiencies calculated for organic carbon (OC, carbon measured as organic multiplied by 1.2) ranged from 3.81 m²/g OC at lower relative humidities (<63%) to 6.90 m²/g OC at higher relative humidities (>75%) while sulfate (assumed as ammonium sulfate) efficiencies ranged from 1.23 m²/g (NH₄)₂SO₄ to 5.78 m²/g (NH₄)₂SO₄ for the same range of relative humidities. Radiative transfer calculations showed that the rural aerosol at Bondville is most likely to have an overall negative (cooling) forcing effect on climate. Elemental carbon (EC), however, acts to counter sulfate forcing to a degree that has a significant seasonal variation, primarily due to the seasonal variation in the sulfate concentrations. Taking the loading to be the mean summer EC+ammonium sulfate loading and assuming [EC]/[(NH₄)₂SO₄] to be zero in one case (i.e. no soot present) and 0.025 (summer mean at Bondville) in another leads to a 37% difference in calculated forcing.     

An instrument for semi-continuous monitoring of the size-distribution of nitrate,ammonium, sulphate and chloride in aerosol

An instrument was developed for semi-continuous measurement of the size-distribution of submicron nitrate, ammonium, sulphate and chloride. Novel in the instrumentation is the size-classification, which is realised with a pre-separator that consists of a set of four parallel impactors. The cut-off diameters of the impactors are at 0.18, 0.32, 0.56 and 1.0 μm. Aerosols smaller than the associated cut-off size pass the respective impactor and arrive in the detector. The manifold with impactors contains two additional lines, one open line and one containing a filter that removes all aerosols. This latter line provides an on-line field-blank. The sample air-flow is automatically switched by wide-bore ball valves to one of the six sampling lines for a period of 20 min; a measuring cycle thus takes 2 h.Down-stream of the pre-separator the sampling and automated on-line analysis of the transmitted aerosol is accomplished with a “MARGA”. In this instrument steam condensation is used to grow the aerosol. The droplets formed are collected in a cyclone that drains to wet-chemical analysis systems. A wet-denuder between pre-separator and collector removes interfering gases, like nitric acid and ammonia. This enables artefact-free and thus representative semi-continuous measurement of the size-distribution of the semi-volatile (ammonium) nitrate.The novel MARGA-sizer was first used in a 1 week field-test. After modifications it was then deployed in a monitoring campaign of 2 months in the summer of 2002, at the top level of the meteo-tower of Cabauw in the centre of the Netherlands. The high location, 200 m, was chosen to obtain data on ammonium nitrate that are minimally affected by surface emissions of ammonia. The data coverage over the period was over 60%; failure of the instrumentation was mainly associated with spells of extreme solar heating of the tower and associated high temperatures inside.The average concentration of nitrate was 2.6 μg m⁻³, which was very similar to the value interpolated from data in the national network. The mass concentration of submicron nitrate was 2.0 μg m⁻³, of which 46% was in particles smaller than 0.32 μm. To put this in perspective: the concentration of submicron sulphate was similar to that of nitrate, while 53% was in particles smaller than 0.32 μm. The ion balance showed that the compounds were present as the fully neutralised salts. Quite large diurnal variations were observed for nitrate, with a surprising maximum in the afternoon. The size-distribution of the semi-volatile nitrate was rather constant over a daily cycle.     

Modeling the spectral optical properties of ammonium sulfate and biomass burning aerosols: parameterization of relative humidity effects and model results

The importance of including the global and regional radiative effects of aerosols in climate models has increasingly been realized. Accurate modeling of solar radiative forcing due to aerosols from anthropogenic sulfate and biomass burning emissions requires adequate spectral resolution and treatment of spatial and temporal variability. The variation of aerosol spectral optical properties with local relative humidity and dry aerosol composition must be considered. Because the cost of directly including Mie calculations within a climate model is prohibitive, parameterizations from off-line calculations must be used. Starting from a log-normal size distribution of dry ammonium sulfate, we developed optical properties for tropospheric sulfate aerosol at 15 relative humidities up to 99%. The resulting aerosol size distributions were then used to calculate bulk optical properties at wavelengths between 0.175 and 4 μm. Finally, functional fits of optical properties were made for each of 12 wavelength bands as a function of relative humidity. Significant variations in optical properties occurred across the total solar spectrum. Relative increases in specific extinction and asymmetry factor with increasing relative humidity became larger at longer wavelengths. Significant variation in single-scattering albedo was found only in the longest near-IR band. This is also the band with the lowest single scattering albedo. A similar treatment was done for aerosols from biomass burning. In this case, two size distributions were considered. One was based on a distribution measured for Northern Hemisphere temperate forest fires while the second was based on a measured size distribution for tropical fires. Equilibrium size distributions and compositions were calculated for 15 relative humidities and five black carbon fractions. Mie calculations and band averages of optical properties were done for each of the resulting 75 cases. Finally, fits were made for each of 12 spectral bands as functions of relative humidity and black carbon fraction. These optical properties result in global average forcing from anthropogenic sulfate aerosols of −0.81 Wm^-2. The global average forcing for biomass aerosols ranged from −0.23 to −0.25 Wm^-2 depending on the assumed size distribution, while fossil fuel organic and black carbon are estimated to heat the atmosphere by about 0.16 Wm^-2.     

Laboratory Characterization of Modified Tapered Element Oscillating Microbalance Samplers

Abstract

Laboratory tests with generated aerosols were conducted to test the efficacy of two recent design modifications to the well-established tapered element oscillating microbalance (TEOM) continuous particulate matter (PM) mass monitor. The two systems tested were the sample equilibration system-equipped TEOM monitor operating at 30 °C, which uses a Nafion dryer as part of the sample inlet, and the differential TEOM monitor, which adds a switched electrostatic precipitator and uses a self-referencing algorithm to determine “true PM mass.” Test aerosols included ammonium sulfate, ammonium nitrate, sodium chloride, copper (II) sulfate, and mixed aerosols. Aerosols were generated with an atomizer or a vibrating orifice generator and were equilibrated in a 450-L slow flow chamber before being sampled. Relative humidity in the chamber was varied between 10 and 90%, and step changes in humidity were executed while generating aerosol to test the response of the instruments. The sample equilibration system-equipped TEOM monitor does reduce, but not totally eliminate, the sensitivity of the TEOM mass monitor to changes in humidity. The differential TEOM monitor gives every indication of being a very robust technique for the continuous real-time measurement of ambient aerosol mass, even in the presence of semi-volatile particles and condensable gases.     

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.     

Simulating the fine and coarse inorganic particulate matter concentrations in a polluted megacity

A three dimensional chemical transport model (PMCAMx) is applied to the Mexico City Metropolitan Area (MCMA) in order to simulate the chemical composition and mass of the major PM₁ (fine) and PM_1–10 (coarse) inorganic components and determine the effect of mineral dust on their formation. The aerosol thermodynamic model ISORROPIA-II is used to explicitly simulate the effect of Ca, Mg, and K from dust on semi-volatile partitioning and water uptake. The hybrid approach is applied to simulate the inorganic components, assuming that the smallest particles are in thermodynamic equilibrium, while describing the mass transfer to and from the larger ones. The official MCMA 2004 emissions inventory with improved dust and NaCl emissions is used. The comparison between the model predictions and measurements during a week of April of 2003 at Centro Nacional de Investigacion y Capacitacion Ambiental (CENICA) “Supersite” shows that the model reproduces reasonably well the fine mode composition and its diurnal variation. Sulfate predicted levels are relatively uniform in the area (approximately 3 μg m^?3), while ammonium nitrate peaks in Mexico City (approximately 7 μg m^?3) and its concentration rapidly decreases due to dilution and evaporation away from the urban area. In areas of high dust concentrations, the associated alkalinity is predicted to increase the concentration of nitrate, chloride and ammonium in the coarse mode by up to 2 μg m^?3 (a factor of 10), 0.4 μg m^?3, and 0.6 μg m^?3 (75%), respectively. The predicted ammonium nitrate levels inside Mexico City for this period are sensitive to the physical state (solid versus liquid) of the particles during periods with RH less than 50%.     

Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.