Gyula Kiss

Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility

A chemical mass balance of fine aerosol (<1.5 μm AED) collected at three European sites was performed with reference to the water solubility of the different aerosol classes of components. The sampling sites are characterised by different pollution conditions and aerosol loading in the air. Aspvreten is a background site in central Sweden, K-puszta is a rural site in the Great Hungarian Plain and San Pietro Capofiume is located in the polluted Po Valley, northern Italy. The average fine aerosol mass concentration was 5.9 μg m-3 at the background site Aspvreten, 24 μg m-3 at the rural K-puszta and 38 μg m-3 at the polluted site San Pietro Capofiume. However, a similarly high soluble fraction of the aerosol (65–75%) was measured at the three sites, while the percentage of water soluble organic species with respect to the total soluble mass was much higher at the background site (ca. 50%) than at the other two sites (ca. 25%). A very high fraction (over 70%) of organic compounds in the aerosol consisted of polar species. The presence of water soluble macromolecular compounds was revealed in the samples from K-puszta and San Pietro Capofiume. At both sites these species accounted for between ca. 20–50% of the water soluble organic fraction. The origin of the compounds was tentatively attributed to biomass combustion.

In-situ formation of light-absorbing organic matter in cloud water

Current climate models seem to underestimate the flux of solar energy absorbed by the global troposphere. All of these models are constrained with the assumption that cloud droplets consist of pure water. Here we demonstrate in a simple laboratory experiment that aromatic hydroxy-acids which are found in continental fine aerosol can react with hydroxyl radicals under typical conditions prevalent in cloud water influenced by biomass burning. The reactions yield colored organic species which do absorb solar radiation. We also suggest that the products of such reactions may be humic-like substances whose presence in continental aerosol has been confirmed but their source mechanisms are still much sought after. We also attempt to give a first order estimate of the enhancement of water absorption at a visible wavelength under atmospheric conditions.

Study on the Chemical Character of Water Soluble Organic Compounds in Fine Atmospheric Aerosol at the Jungfraujoch

In this study the chemical nature of the bulk of water soluble organic compounds in fine atmospheric aerosol collected during summer 1998 at the Jungfraujoch, Switzerland (3580 m asl) is characterised. The mass concentration of water soluble organic substances was similar to those of major inorganic ions, and the water soluble organic matter was found to be composed of two main fractions: (i) highly polyconjugated, acidic compounds with a varying degree of hydrophobicity and (ii) slightly polyconjugated, neutral and very hydrophilic compounds. The contribution of both fractions to the total water soluble organic carbon was about 50%. Separation into individual components was impossible either by HPLC or capillary electrophoresis which indicates the presence of a high number of chemically similar but not identical species. Results obtained by ultrafiltration and HPLC-MS have shown that the molecular weights are of the order of several hundreds. Most of the protonation constants for the acidic compounds determined by capillary electrophoresis were in the range 104–107.

Isolation of water-soluble organic matter from atmospheric aerosol.

The development of a solid phase extraction (SPE) method is presented, which is capable of isolating approx. 60% of the water-soluble organic compounds from aerosol samples. The aqueous extracts of the filter samples were acidified then passed through an SPE column. Four silica-based and two polymeric reversed phase columns were tested and similar recoveries of the organic carbon were found. The isolated organic matter was nearly free from inorganic ions, which are major constituents of atmospheric aerosol. This fraction accounted for a major part of the UV absorption above 250 nm and fluorescence activity of the aerosol extract. The precision of the method was tested by performing three parallel sample preparations with Oasis HLB columns. It was found that the relative standard deviation of the carbon content of the isolated organic matter was better than 7%, which indicated the reliability of the method. In the atmospheric aerosol research the newly developed sample preparation method facilitates the physical and chemical characterisation of water-soluble organic compounds without the interference of inorganic constituents.

Analysis of the Unresolved Organic Fraction in Atmospheric Aerosols with Ultrahigh-Resolution Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy: Organosulfates As Photochemical Smog Constituents†

Complementary molecular and atomic signatures obtained from Fourier transform ion cyclotron resonance (FTICR) mass spectra and NMR spectra provided unequivocal attribution of CHO, CHNO, CHOS, and CHNOS molecular series in secondary organic aerosols (SOA) and high-resolution definition of carbon chemical environments. Sulfate esters were confirmed as major players in SOA formation and as major constituents of its water-soluble fraction (WSOC). Elevated concentrations of SO(2), sulfate, and photochemical activity were shown to increase the proportion of SOA sulfur-containing compounds. Sulfonation of CHO precursors by means of heterogeneous reactions between carbonyl derivatives and sulfuric acid in gas-phase photoreactions was proposed as a likely formation mechanism of CHOS molecules. In addition, photochemistry induced oligomerization processes of CHOS molecules. Methylesters found in methanolic extracts of a SOA subjected to strong photochemical exposure were considered secondary products derived from sulfate esters by methanolysis. The relative abundance of nitrogen-containing compounds (CHNO and CHNOS series) appeared rather dependent on local effects such as biomass burning. Extensive aliphatic branching and disruption of extended NMR spin-systems by carbonyl derivatives and other heteroatoms were the most significant structural motifs in SOA. The presence of heteroatoms in elevated oxidation states suggests a clearly different SOA formation trajectory in comparison with established terrestrial and aqueous natural organic matter.

Determination of polycyclic aromatic hydrocarbons in precipitation using solid-phase extraction and column liquid chromatography

Abstract Solid-phase extraction (SPE) of polycyclic aromatic hydrocarbons (PAHs) on Sep-Pak C 18 cartridges was studied. Eight 3–6-ring compounds from the 16 EPA priority pollutants were selected for investigation. Factors affecting the recovery of PAHs such as conditioning of the SPE cartridge, addition of organic modifier to the sample, flow-rate of the sample loaded on the cartridge, concentration of PAHs in the sample, drying after sample loading, elution of the analytes from the SPE cartridge with different organic solvents and recovery from spiked rainwater were included. Conditioning time was shortened by omitting the application of a 2-propanol-water mixture. The presence of 25% (v/v) 2-propanol was most appropriate for the enrichment of 3–6-ring aromatic compounds on Sep-Pak C 18 . The flow-rate of the sample influenced the efficiency of sample preparation of compounds with a retention volume close to the sample volume. Recoveries did not change significantly in the 20–2200 ng/l concentration range. Drying of the SPE cartridge after sample loading improved recoveries of all PAHs. Elution with dichloromethane and tetrahydrofuran gave the highest recoveries. The detection limit was found to be less than 1 ng/l for several PAHs. The concentrations of PAHs in rainwater were between 3 and 1000 ng/l.

Distribution of polycyclic aromatic hydrocarbons on atmospheric aerosol particles of different sizes

The size distribution of polycyclic aromatic hydrocarbons (PAHs) in aerosol samples collected with a Berner-type nine-stage cascade impactor was determined. Most of the PAHs were found on aerosol particles having aerodynamic diameter between 0.125 and 2 μm. Relationship between meteorological parameters and the size distribution of PAHs as well as the total PAH content of aerosol samples was investigated. Both the overall mass median diameter (MMD) and the total concentration of PAHs increased with decreasing ambient temperature.

The inportance of organic and elemental carbon in the fine atmospheric aerosol particles

During a field campaign the chemical character of fine (d < 2.5 μm) aerosol particles was studied at K-puszta, Hungary within the framework of a project of the European Union. The organic and elemental carbon fraction, as well as the concentration of major inorganic constituents with respect to the total fine aerosol mass are presented in this paper. It was found that organic compounds constituted a significant fraction of the total fine aerosol mass, their contribution is comparable to or larger than that of the major water soluble ions. The diurnal variation of aerosol composition was also studied. It can be concluded that the relative abundance of the major constituents is practically the same during the day and at night. The samples were also classified and studied according to the air mass history. It is stated that the aerosol can be separated into two populations with different regression lines between organic and elemental carbon.

The seasonal changes in the concentration of polycyclic aromatic hydrocarbons in precipitation and aerosol near Lake Balaton, Hungary

The concentration of polycyclic aromatic hydrocarbons (PAHs) in atmospheric precipitation and aerosol samples was monitored in a rural site by Lake Balaton, Hungary to examine the seasonal variation. The seasonal mean concentration of individual 3-6-ring PAHs in precipitation varied from 1 to 54 ng l-1 and from 3 to 350 ng l-1 in summer and winter, respectively. In the atmospheric aerosol samples the seasonal mean concentration of PAHs varied from 4 to 880 pg m-3, from 4 to 300 pg m-3, from 11 to 1050 pg m-3 and from 36 to 5000 pg m-3 in spring, summer, autumn and winter, respectively. Wet (412 micrograms m-2 year-1) and aerosol (190-300 micrograms m2 year-1) deposition rates were also estimated indicating that the two processes are of comparable importance in the removal of 3-6-ring PAHs from the atmosphere.

Electrokinetic injection in capillary electrophoresis and its application to the analysis of inorganic compounds.

In capillary electrophoresis, electrokinetic injection is a highly controversial sampling technique. It is a simple mode of sample introduction which is suitable for on-line preconcentration of the analytes, but its precision and accuracy are more strongly affected by experimental conditions compared to hydrodynamic injection. In the first part of this paper the features of electrokinetic and hydrodynamic injections are compared, followed by a detailed discussion on the different biases of electrokinetic injection and on how to reduce them. Finally, applications of the electrokinetic injection are reviewed with special emphasis on the analysis of inorganic compounds.