Jaroslav Schwarz

Aerosol chemical mass closure during the EUROTRAC-2 AEROSOL Intercomparison 2000

Abstract The field work for the AEROSOL Intercomparison 2000 took place from 4 to 14 April 2000 at Melpitz, Germany. One objective was to assess to which extent aerosol chemical mass closure could be obtained for the site. For this purpose, we operated four filter samplers in parallel (mostly using 12-h collections): two Gent PM10 stacked filter unit (SFU) samplers (one with coarse and fine Nuclepore polycarbonate filters, the other with a Gelman Teflo filter as fine filter) and two single filter holders (one with PM2.5 inlet, the other with PM10 inlet) with Whatman QM-A quartz fibre filters. All samples were analysed for the particulate mass (PM) by weighing; the samples from the first SFU were analysed for 42 elements by a combination of particle-induced X-ray emission spectroscopy and instrumental neutron activation analysis, those from the other SFU for major anions and cations by ion chromatography. All quartz filters were analysed for organic carbon and elemental carbon by a thermal–optical transmission technique. Aerosol chemical mass closure calculations were done for the separate fine (PM2) and coarse (2–10 μm) size fractions. As gravimetric PM data we used the averages from the parallel SFU collections. For reconstituting this PM, nine aerosol types (or components) were considered. Crustal matter, organic aerosol and nitrate were the major aerosol types in the coarse size fraction; the dominant aerosol types in the fine fraction were organic aerosol, nitrate and sulphate. The included components explained 116% and 86% of the gravimetric PM in the coarse and fine size fractions, respectively.

Mass transfer from a drop—II. Theoretical analysis of temperature dependent mass flux correlation

Abstract A new expression of the droplet Sherwood number (Sh) is presented based on the theoretical treatment of the temperature dependent gaseous diffusion coefficient. The experimentally specified parameters were correlated by means of recent data on water droplets evaporating in the flow field. The mass flux correlation is given as a function of the Reynolds (Re) and Schmidt (Sc) numbers, and it turned out to be Sh = (2.009+0.514Re 1 2 Sc 1 3 ) . The Sherwood number should be multiplied by a strictly theoretical correction factor which depends on the droplet and gas temperatures and which is order of 0.9, if the temperature deviation is order of 100 K. The introduction of the correction factor seems to remove a discrepancy existing between the earlier theoretical treatments and experimental data.

Evaporation of ventilated water droplet: connection between heat and mass transfer

Heat and mass transfer from evaporating water droplets has been investigated using a wind tunnel technique. The results were compared with results of other authors and correlated by an empirical fit proposed by Clift, Grace, and Weber (Bubbles, Drops, and Particles, Academic Press, New York, 1978 [Chapters 3 and 5]). It was found that the fit gave reasonably accurate predictions for Reynolds numbers Re ranging from 0 to 400. The accuracy of the obtained expression was tested comparing measured and calculated droplet temperatures. The results agree always within 5% and usually even within 1%. This represents an experimental validation for mass and heat flux expressions commonly used in condensation and evaporation studies.

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.

Markers of oxidative damage of nucleic acids and proteins among workers exposed to TiO2 (nano) particles

Objective The use of nanotechnology is growing enormously and occupational physicians have an increasing interest in evaluating potential hazards and finding biomarkers of effect in workers exposed to nanoparticles. Methods A study was carried out with 36 workers exposed to (nano)TiO2 pigment and 45 controls. Condensate (EBC) titanium and markers of oxidation of nucleic acids (including 8-hydroxy-2-deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8-OHG), 5-hydroxymethyl uracil (5-OHMeU)) and proteins (such as o-tyrosine (o-Tyr), 3-chlorotyrosine (3-ClTyr) and 3-nitrotyrosine (3-NOTyr)) were analysed from samples of their exhaled breath. Results In the production workshops, the median total mass 2012 and 2013 TiO2 concentrations were 0.65 and 0.40 mg/m3, respectively. The median numbers of concentrations measured by the scanning mobility particle sizer (SMPS) and aerodynamic particle sizer (APS) were 1.98×104 and 2.32×104 particles/cm3, respectively; and about 80% of those particles were smaller than 100 nm in diameter. In the research workspace, lower aerosol concentrations (0.16 mg/m3 and 1.32×104 particles/cm3) were found. Titanium in the EBC was significantly higher in production workers (p<0.001) than in research workers and unexposed controls. Accordingly, most EBC oxidative stress markers, including in the preshift samples, were higher in production workers than in the two other groups. Multiple regression analysis confirmed an association between the production of TiO2 and the levels of studied biomarkers. Conclusions The concentration of titanium in EBC may serve as a direct exposure marker in workers producing TiO2 pigment; the markers of oxidative stress reflect the local biological effect of (nano)TiO2 in the respiratory tract of the exposed workers.

Oxidative stress markers are elevated in exhaled breath condensate of workers exposed to nanoparticles during iron oxide pigment production

Markers of oxidative stress and inflammation were analysed in the exhaled breath condensate (EBC) and urine samples of 14 workers (mean age 43  ±  7 years) exposed to iron oxide aerosol for an average of 10  ±  4 years and 14 controls (mean age 39  ±  4 years) by liquid chromatography-electrospray ionization-mass spectrometry/mass spectrometry (LC-ESI-MS/MS) after solid-phase extraction. Aerosol exposure in the workplace was measured by particle size spectrometers, a scanning mobility particle sizer (SMPS) and an aerodynamic particle sizer (APS), and by aerosol concentration monitors, P-TRAK and DustTRAK DRX. Total aerosol concentrations in workplace locations varied greatly in both time and space. The median mass concentration was 0.083 mg m(-3) (IQR 0.063-0.133 mg m(-3)) and the median particle concentration was 66 800 particles cm(-3) (IQR 16,900-86,900 particles cm(-3)). In addition, more than 80% of particles were smaller than 100 nm in diameter. Markers of oxidative stress, malondialdehyde (MDA), 4-hydroxy-trans-hexenale (HHE), 4-hydroxy-trans-nonenale (HNE), 8-isoProstaglandin F2α (8-isoprostane) and aldehydes C6-C12, in addition to markers of nucleic acid oxidation, including 8-hydroxy-2-deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8-OHG), 5-hydroxymethyl uracil (5-OHMeU), and of proteins, such as o-tyrosine (o-Tyr), 3-chlorotyrosine (3-ClTyr), and 3-nitrotyrosine (3-NOTyr) were analysed in EBC and urine by LC-ESI-MS/MS. Almost all markers of lipid, nucleic acid and protein oxidation were elevated in the EBC of workers comparing with control subjects. Elevated markers were MDA, HNE, HHE, C6-C10, 8-isoprostane, 8-OHdG, 8-OHG, 5-OHMeU, 3-ClTyr, 3-NOTyr, o-Tyr (all p  <  0.001), and C11 (p  <  0.05). Only aldehyde C12 and the pH of samples did not differ between groups. Markers in urine were not elevated. These findings suggest the adverse effects of nano iron oxide aerosol exposure and support the utility of oxidative stress biomarkers in EBC. The analysis of urine oxidative stress biomarkers does not support the presence of systemic oxidative stress in iron oxide pigment production workers.

Detailed comparison of OC/EC aerosol at an urban and a rural Czech background site during summer and winter

Winter and summer measurements of organic carbon and elemental carbon (OC and EC) in PM2.5 were performed in parallel at two sites, the rural background station Košetice and the Prague-Suchdol urban background site, with a 2-h time resolution using semi-online field OC/EC analysers. Seasonal and site differences were found in the OC and EC contents of PM2.5. Overall, the highest concentrations of both OC and EC were during winter at the urban site. The average urban impact was 50% for OC and 70% for EC. The summer season gives similar concentrations of OC at both sites. However, higher concentrations of EC, caused by higher traffic, were found at the urban site with an average urban increase of 50%. Moreover, an analysis of four OC fractions depending on the volatility (OC1 - most volatile, OC4 - least volatile) and pyrolytic carbon (PC) is provided. A similar level of each OC fraction at both sites was found in summer, except for higher OC1 at urban and higher PC at the rural site. In winter, the differences between the urban and rural sites were dominated by a large increase of the OC1 fraction in comparison with the rural site. A diurnal pattern of concentration and share of OC1 and PC suggests a prevailing influence of local sources on their concentrations at the urban site in winter. The OC3 and OC4 diurnal cycles suggest their more regional or long range transport origin in both seasons. The prevalent influence of OC1 at any urban site has not been previously reported. The minimisation of semi-volatile carbon losses during semi-continuous sampling and analysis, in comparison with off-line sampling methods, is a probable reason for the observed differences.

Mass and chemically speciated size distribution of Prague aerosol using an aerosol dryer--the influence of air mass origin.

Ambient aerosol particles dried using a diffusional aerosol dryer were sampled using a 7-stage modified Berner low pressure impactor with a back-up filter during the heating and non-heating season campaigns in 2008. The samples were analyzed for water-soluble ions and water-soluble organic carbon. Because of the drying, the aerosol size distribution was not influenced by the daily variability of ambient relative humidity. The results summarize the observations from campaigns in both the heating (11 sampling days) and non-heating (10 sampling days) seasons. The aerosols sampled on individual days were classified based on the connected air mass back trajectories into three classes: sea-influenced aerosol (SIA), continental aerosol (CA) and mixed aerosol (MA) for samples of intermediate origin. The differences between CA and SIA were substantial both when looking at the normalized mass size distributions of the particulate matter (PM) and of the individual species and when taking into account the absolute concentrations in the fine and coarse size fractions. The main differences were found in the normalized mass size distributions of the PM and of the sea-salt related ions.

Study of elemental mass size distributions at Skukuza, South Africa, during the SAFARI 2000 dry season campaign

Abstract As part of the final dry season campaign of SAFARI 2000, a 12-stage small deposit area low pressure impactor (SDI) was operated at Skukuza, in the Kruger National Park, South Africa, from 17 August until 19 September 2000. Separate day and night samples were collected (64 in total), starting at about 7:00 and at about 18:00 local time, respectively. The samples were analysed for 28 elements by PIXE. The total concentrations (summed over all 12 stages) varied quite substantially during the campaign (up to a factor of 50), but no systematic day/night difference pattern was observed. Also the size distributions were rather similar during day and night. S, K, Zn, As, Se, Br, Rb and Pb had most of their mass in the submicrometre size range, with maximum typically at about 0.3 μm equivalent aerodynamic diameter. Several of those elements are good indicators for biomass burning. Mass median aerodynamic diameters (MMADs) were calculated for the various elements and compared with those obtained during SAFARI-92. During this earlier campaign, which also took place in the dry season, 41 daily samples were taken at Skukuza with a PIXE International cascade impactor (PCI). For the crustal and sea-salt elements, fairly similar MMADs were obtained in the two campaigns. For the fine-mode elements, however, the MMADs were substantially lower during SAFARI 2000 than during SAFARI-92. During this earlier campaign, the MMADs were most likely overestimated. Compared to the SDI, the PCI is much less appropriate for studying the size distribution in the submicrometre size range.

Mass transfer from a drop—I. Experimental study and comparison with existing correlations

Abstract An experimental study was conducted to measure the rates of mass transfer from a water drop, suspended from a quartz capillary in a stream of a hot air flowing upward in a vertical wind tunnel. Measurements were made for bulk temperature T∞ = 314–449 K, drop temperature T0 = 287–315 K, free stream velocity U∞ = 0.5 – 1.7 ms−1, drop diameter d = 0.7 – 2.3 mm, dimensionless driving force B = 0.007 – 0.068, Re = 30–180 and Sc = 0.62. The data were compared with results of previous works. It was found that existing correlations proposed for higher mass transfer conditions do not improve experimental data interpretation