S. Nyeki

Separation of volatile and non-volatile aerosol fractions by thermodesorption : instrumental development and applications

Abstract An instrument to remove volatile material from aerosol particles by thermal desorption is presented. The thermodesorber consists of a heated tube, where volatile material is desorbed from the particles, and a water- or air-cooled tube, consisting of activated charcoal. This last tube removes desorbed material and thus prevents it from re-adsorbing onto particles. Although designed for measuring particulate emissions from combustion processes it can also be applied to atmospheric aerosols. After theoretical and experimental determination of thermodesorber operating characteristics (temperature profile, losses, removal of desorbed material), examples of applications in several fields are given. Examples of atmospheric measurements at several remote and urban sites are presented. In combustion technology, the thermodesorber is applied to remove all volatile materials, allowing separation of volatile species and the non-volatile core (mainly elemental carbon) of combustion particles. Finally, the thermodesorber is used to study adsorption and desorption processes of polycyclic aromatic hydrocarbons on particles.

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.

Seasonal and diurnal variation of aerosol size distributions (10<D<750 nm) at a high‐alpine site (Jungfraujoch 3580 m asl)

During an extended field campaign at a high-alpine site (Jungfraujoch; 3580 m asl, Switzerland) from March 1997 to May 1998, the particle number size distribution (diameter D = 18-750 nm) and number concentration N (D > 10 nm) were measured on a continuous basis. The number size distribution was dominated by particles with D < 100 nm, while most of the surface area was in the accumulation mode size range (0.1-1 μm). Average size distributions exhibited a distinct bimodal shape which is generated and maintained by cloud processes and is less distinct in the free troposphere. Fitted modal diameters and standard deviations σ of the Aitken (20-100 nm) and accumulation modes were surprisingly constant throughout the year (D Ait = 43 ± 3 nm; D Acc = 140 ± 6 nm; σ Ait = 2.13 ± 0.11; σ Acc = 1.61 ± 0.03). The relative number concentrations in both modes are responsible for the seasonality observed in the shape of the size distribution. The high seasonality of N Acc with summer and winter values of∼260 and ∼40 cm -3 , respectively, is mainly due to transport of planetary boundary layer air to the station. In contrast, new particle formation is responsible for the high concentrations of nucleation mode particles (D < 20 nm) which exhibited a maximum during the winter months. The relatively low seasonality found for N Ait (summer, winter values: ∼530,∼310 cm -3 ) is due to gas-to-particle conversion as well as transport processes. An analysis showed that a significant fraction of nucleation mode particles were formed by photochemical reactions.

Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

Abstract The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM 2.5 aerosol); (ii) K-puszta, Hungary (rural, PM 1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.

The Jungfraujoch high-alpine research station (3454 m) as a background clean continental site for the measurement of aerosol parameters

The first annual data set of climatically important aerosol parameters, measured at the Jungfraujoch (JFJ) high-alpine research station (3454 m, Switzerland) from an ongoing field campaign since July 1995, is presented. Analysis of diurnal variations in continuous measurements of the total and backward hemispheric scattering coefficients (σSP, σBSP), the absorption coefficient (σAP, from aethalometer data), condensation nuclei (CN) concentration, and epiphaniometer signal (related to surface area (S) concentration) established the diurnal period 0300 – 0900 as being representative of the free tropospheric background aerosol. The annual data set was then edited to omit (1) the period 0900–0300 (i.e., 18 hours), taken to represent possible planetary boundary layer influenced conditions and (2) in-cloud conditions using a cloud liquid-water monitor. The seasonal aerosol cycle exhibited a July maximum and a December minimum in most aerosol parameters. Typical monthly median values for the free troposphere exhibit the following seasonal maxima and minima, respectively: σSP (550 nm) ∼ 16.1 and 0.43 × 10−6 m−1, σBSP (550 nm) ∼ 2.10 and 0.09 × 10−6 m−1, σAP (550 nm) ∼ 10.4 and 0.76 × 10−7 m−1 (≈ 104 and 7.6 ng m−3 black carbon), CN concentration ∼ 670 and 280 cm−3, and epiphaniometer signal ∼ 9.26 and 0.67 counts s−1 (S concentration ≈24.1 and 1.7 μm2 cm−3). Aerosol parameters were found to be comparable in magnitude to other NOAA baseline and regional stations and suggest that a clean continental designation for the JFJ site is applicable, when removing the planetary boundary layer influenced period.

The background aerosol size distribution in the free troposphere: An analysis of the annual cycle at a high‐alpine site

Measurements during free tropospheric (FT) and planetary boundary layer (PBL) conditions were conducted over an annual cycle at the Jungfraujoch high-Alpine research station (3454 m), Switzerland, in order to establish diurnal and seasonal cycles of the background continental aerosol over central Europe. Using a condensation nucleus counter (TSI 3025) and an optical particle counter (PMS Las-X) from June 1996 to May 1997, the following were determined: (1) accumulation mode lognormal parameters and (2) number concentrations for the nucleation (diameter d < 0.1 μm), accumulation (0.1 ≤ d ≤ 1.0 μm), and part of the coarse (1.0 < d ≤ 7.5 μm, designated “coarse”) modes. Lognormal parameters were found to be similar for FT and PBL conditions, and exhibited a weak seasonality in geometric median diameter dGN =0.13 and 0.10 μm, and standard deviation σG = 1.73 and 1.64 for summer and winter, respectively. Aerosol number concentrations in each mode exhibited a more pronounced seasonality, with FT concentrations being lower than those for PBL. Summer and winter FT median concentrations for the nucleation, accumulation, and “coarse” modes were 405 and 195 cm−3, 114 and 26 cm−3, and 0.052 and 0.014 cm−3, respectively. These results provide tentative support of other long-term observations that the FT background aerosol mode appears to vary mainly in concentration rather than accumulation mode shape. Further analysis indicated that only the total concentration in each mode varied with weather type and a classification between that of a remote continental and polar aerosol model was found for the Jungfraujoch.

Influences of vertical transport and scavenging on aerosol particle surface area and radon decay product concentrations at the Jungfraujoch (3454 m above sea level)

Concentrations of the aerosol particle surface area (SA) and aerosol-attached radon decay products 214Pb and 212Pb have been measured by means of an aerosol and a radon epiphaniometer at the Jungfraujoch research station (JFJ; 3454 m above sea level, Switzerland). These parameters exhibit a pronounced seasonal cycle with minimum values in winter and maximum values in summer. In summer, pronounced diurnal variations with a maximum at 1800 LST are often present. Highest concentrations and most pronounced diurnal variations occur during anticyclonic weather conditions in summer. Thermally driven vertical transport over alpine topography is responsible for this observation. During this synoptic condition, concentrations vary greatly with the 500 hPa wind direction, exhibiting low concentrations for NW-N winds and high concentrations for weak or S-SW winds. Lead-214 and SA are highly correlated during anticyclonic conditions, indicating transport equivalence of the gaseous 214Pb precursor, 222Rn, and of aerosol particles. When cyclonic lifting is the dominant vertical transport, wet scavenging of aerosol particles can explain the weak correlation of 214Pb and SA. This conclusion is corroborated by the 214Pb/SA ratio, being twice as high during cyclonic than during anticyclonic conditions. Lead-212 is a tracer for the influence of surface contact on a local scale due to its short lifetime of 15.35 hours. The analysis of this parameter suggests that high-alpine surfaces play an important role in thermally driven transport to the JFJ.