Imre Salma

Regional atmospheric aerosol composition and sources in the eastern Transvaal, South Africa, and impact of biomass burning

As part of the Southern Africa Fire-Atmosphere Research Initiative (SAFARI-92), size-fractionated aerosol samples were collected during September–October 1992 at three fixed ground-based sites in the eastern Transvaal, i.e., at two sites within the Kruger National Park (KNP) and at a third site on the Transvaal highveld (about 150 km WSW of the KNP sites), and near a number of prescribed fires in the KNP. The collection devices consisted of stacked filter units, which separate the aerosol into a coarse (2–10 μm equivalent aerodynamic diameter (EAD)) and a fine (<2 μm EAD) size fraction, and of eight-stage cascade impactors, which provide more detailed size fractionation. The samples were analyzed for particulate mass (PM), black carbon (BC), and up to 47 elements. The prescribed fires gave rise to high levels of airborne soil dust, but several species (elements) were particularly enriched in the pyrogenic emissions. This was the case for BC, P, K, Ca, Mn, Zn, Sr, and I in the coarse fraction, and for BC, the halogens (Cl, Br, I), K, Cu, Zn, Rb, Sb, Cs, and Pb (and in the flaming phase also Na and S) in the fine fraction. The aerosol concentrations, compositions, and time trends at the two KNP sites were quite similar, suggesting that regionally representative samples were collected. Receptor modeling calculations, using both absolute principal component analysis and chemical mass balance, indicated that the KNP coarse PM was essentially attributable to mineral dust and sea salt, with average relative apportionments of 75% and 25%, respectively. At the highveld site, mineral dust and sea salt contributed in a 99-to-1 ratio to the coarse PM. In the fine size fraction at all three fixed sites, four components were identified, i.e., mineral dust, sea salt, biomass burning products, and sulfate. The pyrogenic component was the dominant contributor to the atmospheric concentrations of BC, K, Zn, and I, a major source for PM, Cl, Cu, Br, and Cs, but only a minor source for S. About 40% of the fine PM was, on the average, attributed to the pyrogenic particles, and about one third of it to the sulfate component. Relation of the time trends of the various components with three-dimensional air mass back trajectories indicated that elevated levels of pyrogenic products were mostly found in air masses arriving from the north. The levels of the sulfate component tended to be higher at the highveld site than at the two KNP sites, and this component was generally associated with continental air. It was concluded that the major contribution to this fine sulfate came from fossil fuel burning and various industrial activities on the Transvaal highveld.

Comprehensive characterisation of atmospheric aerosols in Budapest, Hungary: physicochemical properties of inorganic species

Abstract As part of an air pollution project in Budapest, aerosol samples were collected by stacked filter units and cascade impactors at an urban background site, two downtown sites, and within a road tunnel in field campaigns conducted in 1996, 1998 and 1999. Some criteria pollutants were also measured at one of the downtown sites. The aerosol samples were analysed by one or more of the following methods: instrumental neutron activation analysis, particle-induced X-ray emission analysis, a light reflection technique, gravimetry, thermal profiling carbon analysis and capillary electrophoresis. The quantities measured or derived include atmospheric concentrations of elements (from Na to U), of particulate matter, of black and elemental carbon, and total carbonaceous fraction, of some ionic species (e.g., nitrate and sulphate) in the fine ( μm equivalent aerodynamic diameter, EAD) or in both coarse (10– 2 μm EAD) and fine size fractions, atmospheric concentrations of NO, NO2, SO2, CO and total suspended particulate matter, and meteorological parameters. The analytical results were used for characterisation of the concentration levels, elemental composition, time trends, enrichment of and relationships among the aerosol species in coarse and fine size fractions, for studying their fine-to-coarse concentration ratios, spatial and temporal variability, for determining detailed elemental mass size distributions, and for examining the extent of chemical mass closure.

Chemical characterisation of humic-like substances from urban, rural and tropical biomass burning environments using liquid chromatography with UV/vis photodiode array detection and electrospray ionisation mass spectrometry

Environmental context One of the most important classes of water-soluble organic compounds in continental fine and tropical biomass burning aerosol is humic-like substances (HULIS), which contain components with strong polar, acidic and chromophoric properties. We focus on the chemical characterisation of HULIS and provide evidence that nitro-aromatic catecholic compounds are among the major species of HULIS. This indicates that volatile aromatic hydrocarbons emitted during biomass burning are important gas-phase precursors for HULIS. Abstract Humic-like substances (HULIS) are ubiquitously present in the troposphere and make up a major fraction of continental fine-sized water-soluble organic compounds. They are regarded as material with strong polar, acidic and chromophoric properties; however, structural information at the individual component level is rather limited. In the present study, we have characterised HULIS from different locations using liquid chromatography coupled to photodiode array detection and negative ion electrospray ionisation mass spectrometry. Aerosol samples with particles less than 2.5 μm in diameter (PM2.5) were collected in Budapest and K-puszta, Hungary, during 2007 and 2008 spring and summer periods, and in Rondonia, Brazil, during a 2002 biomass burning experiment. Major components of the Budapest 2007 and Brazil 2002 HULIS corresponded to chromophoric substances, of which 4-nitrocatechol (molecular weight (MW) 155) was identified as the most abundant organic species and less abundant ones were attributed to mono- and dimethyl nitrocatechols (MWs 169 and 183). The mass concentrations of 4-nitrocatechol in the water-soluble organic carbon (WSOC) of the Budapest 2007 and day- and night-time Brazil 2002 HULIS were 0.46, 0.50 and 1.80 %. Abundant components of K-puszta 2008 HULIS were assigned to α-pinene secondary organic aerosol (SOA) tracers, i.e. 3-methyl-1,2,3-butanetricarboxylic acid and terpenylic acid; their mass concentrations in the HULIS WSOC were 0.75 and 0.40 %. Tere- and ortho-phthalic acids (MW 166) were major components of the Budapest and K-puszta HULIS, but only minor ones of the Brazil 2002 biomass burning HULIS, consistent with a source that is different from biomass burning and likely related to open waste burning of phthalate ester-containing material such as plastic.

Comparative study of elemental mass size distributions in urban atmospheric aerosol

Elemental mass size distributions in aerosols collected at four different urban sites with gradually increasing overall aerosol mass concentration are presented, compared and discussed in the present paper. The aerosol samples were collected with cascade impactor and stacked filter unit samplers, and were analyzed by particle-induced X-ray emission spectrometry and instrumental neutron activation analysis. Typical coarse-mode elements, i.e., Na, Mg, Al, Si, P, Ca, Ti, Fe, Ga, Sr, Zr, Mo and Ba, exhibited unimodal size distributions at all four urban locations studied, and the mass median aerodynamic diameters were increased with aerosol pollution level. Elements typically related to high-temperature or anthropogenic sources, i.e., S, Cl, K, V, Cr, Mn, Ni, Cu, Zn, Ge, As, Se, Br, Rb and Pb, either had a unimodal size distribution with most or their mass in the fine size fraction or clearly showed a bimodal size distribution at the urban background site. However, significant differences between the size distributions of four sampling sites were noted. There was a clear tendency for the accumulation mode to decrease and for the coarse mode to increase with increasing total aerosol mass concentration. A pronounced resuspension of the soil and roadway dust associated with the fine aerosol particles that were deposited on the ground surface previously, and the condensation process of volatile precursor gases on the already existing aerosol particles can explain the observed tendencies. The elemental mass size distributions derived for the polluted urban environments differ from those typically observed for industrial, combustion or automotive sources. A consequence of the diversity in the size distributions on the PM2.5 speciation concept is also presented.

Effect of particle mass size distribution on the deposition of aerosols in the human respiratory system

Elemental mass size distributions were experimentally determined in atmospheric aerosols collected at four different locations in Budapest, Hungary, comprising a urban background site, two downtown sites and a road tunnel. Based on these distributions, deposition fractions for the various elements in the respiratory system were calculated for a healthy Caucasian adult male, female and 5-year-old child under sitting breathing conditions by a stochastic lung deposition model. The highest deposition values were observed in the extrathoracic region regardless of subjects age and gender, and chemical species and size distributions. Deposition in the tracheobronchial tree and acinar region was much smaller than that in the extrathoracic region. Variations in the deposition fractions due to differences in the size distributions were really significant only in the extrathoracic region. Surprisingly, the different size distributions yielded similar depositions in the thoracic region for a given gender as far as the shape of the deposition curve and the total amount are concerned. Regional deposition fractions were compared for the male, female and child, and for various size distributions (sampling location) and elements.

Comparison of particulate number concentrations in three Central European capital cities

Number size distributions of atmospheric aerosol particles in the mobility diameter range from 10 to 1000 nm were determined in Budapest, Prague and Vienna for a one-year-long period. Particle number concentrations in various size fractions, their diurnal and seasonal variations, mean size distributions and some properties of new particle formation events were derived and compared. Yearly median particle number concentrations for Budapest, Prague and Vienna were 10.6×10(3), 7.3×10(3) and 8.0×10(3) cm(-3). Differences were linked to the different pollution levels of the cities, and to diverse measurement environments and local conditions. Mean contributions of ultrafine particles (particles with a mobility diameter <100 nm) to the total number concentration were 80%, 84% and 74% for Budapest, Prague and Vienna, thus these particles represent an overwhelming share of all particles in each city. Seasonal variation of particle number concentrations was not obvious. Diurnal variations of particles with a diameter between 100 and 1000 nm (N(100-1000)) exhibited similar shape for the cities, which was related to the time-activity pattern of inhabitants and regional influences. The structure of the diurnal variation for ultrafine particles was also similar. It contained a huge morning peak in each city which was explained by emissions from vehicular traffic. The second peak was shifted from afternoon rush hours to late evenings as a result of the daily cycling in meteorological parameters. The character of the measurement site also influenced the diurnal variation. Diurnal variation of the mean ratio of ultrafine particles to N(100-1000) clearly revealed the presence and importance of new particle formation and subsequent growth in urban environments. Nucleation frequencies in Budapest and Prague were 27% and 23%, respectively on a yearly time scale. They showed a minimum in winter for both places, while the largest nucleation activity was observed in spring for Budapest, and in summer for Prague.

Effect of physical exertion on the deposition of urban aerosols in the human respiratory system

Abstract Deposition of element-specific particulate matter in the respiratory system of a Caucasian-type healthy adult male and female was computed by a stochastic lung deposition model for different reference levels of physical exertion using mass size distributions in the aerodynamic diameter interval of 0.125– 16 μm experimentally determined in urban environments. Particles with an aerodynamic diameter smaller than about 0.3 μm are deposited in the whole respiratory system decreasingly with rising physical exertion, while the opposite is observed for particles with an aerodynamic diameter larger than about 0.7 μm (except for the highest physical activity). It is the light exercise that causes the largest extrathoracic (ET) deposition efficiency of the particles in this last diameter range, and, consequently, the smallest tracheobronchial and acinar depositions. The results obtained indicate that ET deposition depends primarily on the size distribution of the inhaled particles, while physical exertion plays a minor role. In contrast, deposition fractions of different aerosol species in the lungs are very similar to each other for a given physical exertion, despite the rather diverse size distributions of some species, but depend significantly on the subjects physical exertion. The differential deposition curves generally exhibit two peaks, one in the tracheobronchial and one in the acinar region. Both differential and regional deposition fractions do not change in a monotonical fashion with physical exertion but display maximum values approximately at the exertion level corresponding to the switching point between the nose-breathing mode and the combined nose- and mouth-breathing mode. Deposition rates (mass doses), however, increase monotonically with physical exertion due to increased ventilation rates, and more particles reach the deeper parts of the lung.

Combined application of INAA and PIXE for studying the regional aerosol composition in Southern Africa

As part of the SAFARI-92 biomass buming experiment, aerosol collections were carried out with several size-fractionating sampling devices at a number of sites in Southern Africa. One of the samplers used at all ground-based sites was a stacked filter unit (SFU). The SFU samples were analyzed by both INAA and PIXE analysis. The present paper gives an intercomparison of the analytical results obtained in order to assess the accuracy and to check the quality assurance of the analytical procedures. Twenty-one common elements were determined by both INAA and PIXE. Concentrations of 13 elements (i.e., Na, Mg, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Br) were generally measured with sufficient precision in both techniques for performing the intercomparison. The INAA and PIXE data were compared in terms of PIXE/INAA concentration ratios on a sample by sample basis for the coarse and fine size fraction separately. the atmospheric concentrations for K, Mn and Fe agreed within 5–10%, the agreement between the data for the other common elements was typically better than 15%. Possible explanations for lower than 1.0 ratios for Cl, Br and Na are presented. The common elements were classified into groups according to their detectability and sensitivity in each technique.

Impact of phase out of leaded gasoline on the air quality in Budapest

Abstract As part of an air pollution study in Budapest, size-fractionated aerosol samples were collected by stacked filter units and cascade impactors, and some criteria pollutants and meteorological parameters were recorded in 1996, 1998 and 1999. The samplings were performed at three urban locations including an urban background site, a downtown site, and a tunnel. Elemental composition of the aerosol samples was measured by instrumental neutron activation analysis and/or particle-induced X-ray emission spectrometry; and black carbon (BC) was determined by a light reflectance technique. Since leaded gasoline was completely phased out in Hungary on 1 April 1999, the atmospheric concentrations of some typical transportation-related air pollutants (i.e. Pb, Br, BC and CO) were used for overviewing the actual impact of the phase out on the air quality and on the aerosol characteristics. For the background site, mean concentration of Pb and Br was not changed significantly. In the downtown site, the phase out resulted in a concentration decrease by a factor of 3–4 for Pb and Br. For the tunnel, concentrations of Pb and Br were decreased by a factor up to 9 and 28, respectively. Correlation between the pollutants, their crustal enrichment factors, and average elemental mass size distributions are also presented and discussed.

Connecting hygroscopic growth at high humidities to cloud activation for different particle types

This work recompiles studies that have been done with respect to hygroscopic growth in the regime of high relative humidities and with respect to activation for different kinds of particle at LACIS (Leipzig Aerosol Cloud Interaction Simulator) during the last few years. The particles examined consisted of a mixture of succinic acid and ammonium sulfate, seawater samples, soot coated with an organic and/or an inorganic substance, and two different atmospheric HULIS (HUmic LIke Substance) samples. An influence of changing non-ideal behavior and of slightly soluble substances on the hygroscopic growth was found in varying degrees in the subsaturation regime. The measured hygroscopic growth was extrapolated towards supersaturation, using a simple form of the Kohler equation, and assuming a constant number of molecules/ions in solution for high relative humidities (>= 95% or >= 98%, depending on the particles). When the surface tension of water was used, the modeled critical supersaturations reproduced the measured ones for the seawater samples and for the coated soot particles. To reach agreement between measured and modeled critical supersaturations for the HULIS particles, a concentration-dependent surface tension had to be used, with values of the surface tension that were lower than that of water, but larger than those that had been reported for bulk measurements in the past.