Odor, gaseous and PM10 emissions from small scale combustion of wood types indigenous to Central Europe.

In this study, we investigated the emissions, including odor, from log wood stoves, burning wood types indigenous to mid-European countries such as Austria, Czech Republic, Hungary, Slovak Republic, Slovenia, Switzerland, as well as Baden-Württemberg and Bavaria (Germany) and South Tyrol (Italy). The investigations were performed with a modern, certified, 8 kW, manually fired log wood stove, and the results were compared to emissions from a modern 9 kW pellet stove. The examined wood types were deciduous species: black locust, black poplar, European hornbeam, European beech, pedunculate oak (also known as "common oak"), sessile oak, turkey oak and conifers: Austrian black pine, European larch, Norway spruce, Scots pine, silver fir, as well as hardwood briquettes. In addition, "garden biomass" such as pine cones, pine needles and dry leaves were burnt in the log wood stove. The pellet stove was fired with softwood pellets. The composite average emission rates for log wood and briquettes were 2030 mg MJ-1 for CO; 89 mg MJ-1 for NOx, 311 mg MJ-1 for CxHy, 67 mg MJ-1 for particulate matter PM10 and average odor concentration was at 2430 OU m-3. CO, CxHy and PM10 emissions from pellets combustion were lower by factors of 10, 13 and 3, while considering NOx - comparable to the log wood emissions. Odor from pellets combustion was not detectable. CxHy and PM10 emissions from garden biomass (needles and leaves) burning were 10 times higher than for log wood, while CO and NOx rise only slightly. Odor levels ranged from not detectable (pellets) to around 19,000 OU m-3 (dry leaves). The odor concentration correlated with CO, CxHy and PM10. For log wood combustion average odor ranged from 536 OU m-3 for hornbeam to 5217 OU m-3 for fir, indicating a considerable influence of the wood type on odor concentration.

Indoor and outdoor atmospheric fungal spores in the São Paulo metropolitan area (Brazil): species and numeric concentrations.

The aim of this study was to estimate the indoor and outdoor concentrations of fungal spores in the Metropolitan Area of Sao Paulo (MASP), collected at different sites in winter/spring and summer seasons. The techniques adopted included cultivation (samples collected with impactors) and microscopic enumeration (samples collected with impingers). The overall results showed total concentrations of fungal spores as high as 36,000 per cubic meter, with a large proportion of non culturable spores (around 91% of the total). Penicillium sp. and Aspergillus sp. were the dominant species both indoors and outdoors, in all seasons tested, occurring in more than 30% of homes at very high concentrations of culturable airborne fungi [colony forming units(CFU) m(-3)]. There was no significant difference between indoor and outdoor concentrations. The total fungal spore concentration found in winter was 19% higher than that in summer. Heat and humidity were the main factors affecting fungal growth; however, a non-linear response to these factors was found. Thus, temperatures below 16 degrees C and above 25 degrees C caused a reduction in the concentration (CFU m(-3)) of airborne fungi, which fits with MASP climatalogy. The same pattern was observed for humidity, although not as clearly as with temperature given the usual high relative humidity (above 70%) in the study area. These results are relevant for public health interventions that aim to reduce respiratory morbidity among susceptible populations.

Improved source assessment of Si, Al and related mineral components to PM10 based on a daily sampling procedure.

Samples obtained from an industrialized valley in the East Alpine region were collected daily for a half year and analyzed using X-ray fluorescence to examine the elements Si, Al, Fe, Ca, Mg, Na, K, Zn, P, S and Cl. Some factors affecting the changes of these elements were considered, including time, elemental correlations, weekday, weekend and seasonal changes. Diagnostic analysis provided an insight into a decoupling behavior that occursin siliceous and carbonates minerals. A decrease in Si and Al and an increase in carbonates, Na, K, Zn and P were observed during the cold season. However, a consistently high correlation of Si and Al was observed in all seasons. It was established that such high levels originated from street surface abrasion. The increase in variability and absolute levels of carbonates during the cold season was demonstrated by adding carbonates to the street surface as gritting material to increase the grip on snowy surfaces. A marked increase in Na and Cl was observed in winter which may have been caused by thaw salt that is widely used in winter in Austria. This was associated with a significant increase in K, Zn, and P in the cold season that was the result of domestic space heating with wood. PM10 levels in December were 12 microg/m3 and were higher than levels detected in July. It was established that such high levels originated from mineral oxides, wood smoke, and inorganic ionic material(s).

Determination of saccharides in atmospheric aerosol using anion-exchange high-performance liquid chromatography and pulsed-amperometric detection.

An improved method is described for the quantification of primary sugars, sugar alcohols and anhydrosugars in atmospheric aerosols, making use of separation by high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD). Quartz fibre filters from high-volume samplers were extracted with water and the extract injected directly. Repeatability is typically 4% RSD, for e.g. levoglucosan at 50 ng m(-3) in air, better for winter levels around 700 ng m(-3). Limits of detection for individual sugars are in the range 0.02-0.05 microg mL(-1) in solution, corresponding to 2-5 ng m(-3) from a 20 m(3) air sample. The overlap of arabitol and levogluocosan is overcome by using a Dionex PA-1 column, with appropriate control of eluent composition, and peak deconvolution software, allowing quantification of both sugars in difficult summer samples containing low-levels of levoglucosan. Analysis of a set of ambient aerosol samples by both GC-flame ionization detection and HPAEC-PAD shows good agreement. The new method has the advantage of requiring no sample pretreatment or derivatization and is thus well suited to handling large numbers of samples.

Altitude-dependent wet, dry and occult nitrogen deposition in an Alpine region (Achenldrch, Austria, 920 m - 1758 m a.s.l.).

From November 1995 to October 1996 and from October 1997 to September 1998, samples of wet precipitation, cloud water as well as of reactive gases and particulate matter, were collected at three elevational levels (920 m, 1,280 m and 1,758 m a.s.l.) in Achenkirch, Austria. The samples were analysed for ammonium and nitrate in wet precipitation and in cloud water, for ammonia, nitric acid and nitrogen dioxide in the gas phase and for particulate ammonium and particulate nitrate in aerosol. Total nitrogen deposition was calculated combining measured concentrations in wet, dry and occult depositions with the corresponding deposition fluxes. Two multilayer deposition models were used for the calculation of dry and occult deposition. The total nitrogen input in 1995/96 was estimated to be 29 kg N ha(-1)a(-1) at the Christlumkopf station (1,758 m), 20 kg N ha(-1)a(-1) at the Christlumalm station (1,280 m) and 28 kg N ha(-1)a(-1) at the Talboden station (930 m). Respective data for the 1997/98 observation period were 31 kg N ha(-1)a(-1) at the Christlumkopf station (1,758 m) and 18 kg N ha(-1)a(-1) at the Mülhleggerköpfl station (920 m). Critical Loads of nitrogen for coniferous forests were exceeded significantly near-source regions represented by areas of intense agricultural use and at high elevation sites.

Multidimensional modeling of aerosol monitoring data.

The present study deals with the application of N-way factor analysis for modeling and interpretation of a three-dimensional environmental data set acquired from monitoring of particulate matter (PM) collected at four different sampling locations in Lower Austria region (Central Europe). In the study the Tucker3 algorithm for N-way modeling was used. It was statistically validated that the Tucker3 model offered having the dimensionality [222] is appropriate for correct interpretation of the relationships between chemical parameters, sampling locations and sampling period. The Tucker3 model allowed to distinguish three major sources of pollution in the region of interest conditionally named "soil dust", "combustion" and "street dust" latent factors as responsible for chemical profile of PM and to identify seasonal variability. Additionally, some specificity of the sampling locations was also pointed out.

Application of the integrating sphere method to separate the contributions of brown and black carbon in atmospheric aerosols.

Until about a decade ago, black carbon (BC) was thought to be the only light absorbing substance in the atmospheric aerosol except for soil or desert dust In more recent years, light absorbing polymeric carbonaceous material was found in atmospheric aerosols. Absorption increases appreciably toward short wavelengths, so this fraction was called brown carbon. Because brown carbon is thermally rather refractory, it influences the split between organic carbon (OC) and elemental carbon (EC) in thermal methods and, through its light absorption characteristics, leads to overestimations of BC concentrations. The goal of the present study was to extend the integrating sphere method to correct the BC signal for the contribution of brown carbon and to obtain an estimate of brown carbon concentrations. Humic acid sodium salt was used as proxy for brown carbon. The extended method is first tested on mixtures of test substances and then applied to atmospheric samples collected during biomass smoke episodes (Easter bonfires) in Austria. The resulting concentrations of black and brown carbon are compared to EC obtained with a widely used thermal method, the Cachier method (Cachier et al. Tellus 1989, 41B, 379-390) and a thermal-optical method (Schmid et al. Atmos. Environ. 2001, 35, 2111-2121), as well as to concentrations of humic like substances (HULIS) and to biomass smoke POM (particulate organic matter). Both the thermal methods were found to overestimate BC on days with large contributions of woodsmoke, which agrees with the findings of the method intercomparison study by Reisinger et at. (Environ. Sci. Technol. 2008, 42, 884-889). During the days of the bonfires, the Cachier method gave EC concentrations that were higher by a factor of 3.8 than the BC concentrations, while the concentrations obtained with the thermal-optical method were higher by a factor of 2.6.

Source attribution of submicron organic aerosols during wintertime inversions by advanced factor analysis of aerosol mass spectra.

Real-time measurements of submicrometer aerosol were performed using an Aerodyne aerosol mass spectrometer (AMS) during three weeks at an urban background site in Zurich (Switzerland) in January 2006. A hybrid receptor model which incorporates a priori known source composition was applied to the AMS highly time-resolved organic aerosol mass spectra. Three sources and components of submicrometer organic aerosols were identified: the major component was oxygenated organic aerosol (OOA), mostly representing secondary organic aerosol and accounting on average for 52-57% of the particulate organic mass. Radiocarbon (14C) measurements of organic carbon (OC) indicated that approximately 31 and approximately 69% of OOA originated from fossil and nonfossil sources, respectively. OOA estimates were strongly correlated with measured particulate ammonium. Particles from wood combustion (35-40%) and 3-13% traffic-related hydrocarbon-like organic aerosol (HOA) accounted for the other half of measured organic matter (OM). Emission ratios of modeled HOA to measured nitrogen oxides (NOx) and OM from wood burning to levoglucosan from filter analyses were found to be consistent with literature values.

Combined determination of the chemical composition and of health effects of secondary organic aerosols: the POLYSOA project.

Epidemiological studies show a clear link between increased mortality and enhanced concentrations of ambient aerosols. The chemical and physical properties of aerosol particles causing these health effects remain unclear. A major fraction of the ambient aerosol particle mass is composed of secondary organic aerosol (SOA). Recent studies showed that a significant amount of SOA consists of high molecular weight compounds (oligomers), which are chemically not well characterized. Within the POLYSOA project a large variety of state-of-the-art analytical chemical methods were used to characterize the chemical composition of SOA particles with emphasis on the oligomeric mass fraction. Mass spectrometric results showed that SOA oligomers are highly oxidized compounds and that hydroperoxides are formed, which is consistent with NMR results. This high molecular weight fraction accounts for up to 23% of the total organic carbon in SOA particles. These well-characterized SOA particles were deposited on three lung cell culture systems (microdissected respiratory epithelia from porcine tracheae, the human bronchial epithelial cell line BEAS-2B, and porcine lung surface macrophages obtained by bronchoalveolar lavage) in a newly constructed particle deposition chamber with the goal to eventually identify particle components that are responsible for cell responses leading to adverse health effects. In addition, monolayers of the alveolar epithelial cell line A549 were used in an alveolar epithelial repair model. The lung cells were examined for morphological, biochemical, and physiological changes after exposure to SOA. Analyses of the lung cells after exposure to SOA are ongoing. First data give evidence for a moderate increase of necrotic cell death as measured by lactate dehydrogenase release and for effects on the alveolar epithelial wound repair mainly due to alterations of cell spreading and cell migration at the edge of the wound. Thus, these first results indicate that SOA, in concentrations comparable to environmental concentrations, may induce distinct effects in lung cells.

Carbon-specific analysis of humic-like substances in atmospheric aerosol and precipitation samples.

A new approach for the carbon-specific determination of humic-like substances (HULIS) in atmospheric aerosols is presented. The method is based on a two-step isolation procedure of HULIS and the determination of HULIS carbon with a dissolved organic carbon analyzer. In the first step, a C18 solid-phase extraction is performed to separate HULIS from inorganic and hydrophilic organic sample constituents in aqueous sample solutions. The second isolation step is conducted on a strong anion exchanger to separate HULIS from remaining carbonaceous compounds. This ion chromatographic separation step including the subsequent on-line detection of HULIS carbon was performed fully automated to avoid the risk of sample contamination and to enhance the reproducibility of the method. With a 5-mL sample volume, a limit of detection of 1.0 mg C/L was obtained; this corresponds to an absolute amount of 5 microg of HULIS carbon. The reproducibility of the method given as the relative standard deviation was 4.3% (n = 10). The method was applied for the determination of water-soluble HULIS in airborne particulate matter. PM10 concentrations at an urban site in Vienna, Austria, ranged from around 0.1 to 1.8 microg of C/m(3) (n = 49); the fraction of water-soluble HULIS in OC was 12.1 +/- 7.2% (n = 49).

Aerosol chemical characteristics of an island site in the Bay of Bengal (Bhola-Bangladesh).

Aerosol constituents (elemental carbon, organic carbon, soluble ions including organic acids, and selected trace metals) were investigated from samples of a field campaign taking place at Bhola Island in the Bay of Bengal (Bangladesh). The campaign took place in the pre-monsoon season (May 2001) using low volume samplers. Carbonaceous material comprised the majority of the analysed components. The average concentrations of EC and OC were 2.8 and 4.6 microg m(-3), respectively. Oxalic acid was the most abundant dicarboxylic acid (average 268 ng m(-3)) followed by malonic and malic acid. The contribution of carboxylic acids-carbon to organic carbon was 2.0%. Average concentrations observed for sulfate and nitrate were 3.7 microg m(-3) and 1.5 microg m(-3). Two different types of aerosol were identified at the rural background site on Bhola Island during southerly synoptic flow by means of trajectory analysis: air masses were transported from the Bay of Bengal to the sampling site in all cases. However, during "Period 1" they experienced longer residence times over the Indian Ocean, while the "Period 2" trajectories came along the Indian coast or passed over the Indian continent. During Period 1 the concentration levels of soluble ions were a factor of 4-6 lower than during Period 2. The concentrations of EC, OC and K differed less than a factor of 1.5 between the two periods. The Period 1 aerosol showed similarities to the haze layers observed during winter-monsoon conditions south of India during the INDOEX experiment. Based on EC/TC and K/EC ratios we find that around 80% of the carbonaceous aerosol from Period 1 in Bhola is from fossil fuel and only around 50% from Period 2. Absolute concentrations of carbonaceous species, soluble ions and trace metals indicate that the background site on Bhola Island is affected by emissions from urbanized regions of Southeast Asia.

Determination of the carbon content of airborne fungal spores.

Airborne fungal spores contribute potentially to the organic carbon of the atmospheric aerosol, mainly in the "coarse aerosol" size range 2.5-10 microm aerodynamic equivalent diameter (aed). Here, we report about a procedure to determine the organic carbon content of fungal spores frequently observed in the atmosphere. Furthermore, we apply a new (carbon/individual) factor to quantify the amount of fungal-spores-derived organic carbon in aerosol collected at a mountain site in Austria. Spores of representatives of Cladosporium sp., Aspergillus sp., Penicillium sp., and Alternaria sp., the four predominant airborne genera, were analyzed for their carbon content using two different analytical procedures. The result was an average carbon content of 13 pg C/spore (RSD, 46%), or expressed as a carbon-per-volume ratio, 0.38 pg C/microm3 (RSD, 30%). These values are comparable to conversion factors for bacteria and some representatives of the zooplankton. Because biopolymers are suspected of interfering with elemental carbon determination by thermal methods, the amount of "fungal carbon" that might be erroneously mistaken for soot carbon was determined using the "two-step combustion" method of Cachier et al. and termed as "apparent elemental carbon" (AEC). This fraction amounted to up to 46% of the initial fungal carbon content. Although the aerosol samples were collected in March under wintry conditions, the organic carbon from fungal spores amounted to 2.9-5.4% of organic carbon in the "coarse mode" size fraction.

Monitoring ammonia in urban, inner alpine and pre-alpine ambient air.

Passive samplers were used to monitor ammonia concentrations at rural inner alpine and pre-alpine, as well as urban, sites in Austria and Bavaria. Elevated concentrations were measured both at farms (up to 36 microg NH3 m(-3)) and at urban locations (up to 28 microg NH3 m(-3)). At urban locations a linear relationship between the traffic density and the NH3 concentration was found, but there was no marked seasonal trend. The highest ammonia concentrations were measured in a traffic tunnel (up to 78 microg NH3 m(-3)). The presence of livestock breeding or small scale alpine pastures resulted in elevated concentrations at the rural sites (8.1-12 and 2.5-4.6 microg NH3 m(-3), respectively), compared to the surrounding areas (3.1 and 0.9 microg NH3 m(-3)). Agriculture related sources are usually limited either spatially or seasonally. As the emissions were moderate in our case, a rapid removal and dilution of ammonia was possible and therefore the NH3 burden was only local. Sources related to traffic are more evenly distributed both geographically and seasonally. The WHO guideline, annual average concentration of 8 microg m(-3) for the protection of vegetation, was only exceeded at farms, at the urban station with the heaviest traffic and in the Tauerntunnel.

Combination of sorption tube sampling and thermal desorption with hollow waveguide FT-IR spectroscopy for atmospheric trace gas analysis: determination of atmospheric ethene at the lower ppb level.

The determination of organic trace gases in the ambient environment at the lower ppb level is demonstrated based on a novel technique combining sorption tube sampling on Molsieve and Carbosieve S-III, thermal desorption, and detection of the trace analyte by hollow waveguide Fourier transform infrared (HWG-FT-IR) spectroscopy. While ethene concentrations of approximately 5 ppm can be directly observed using HWG-FT-IR, enrichment factors of up to 5000 were achieved by sorption tube sampling and thermal desorption. Detection limits of approximately 1 ppb are reported. Efficient enrichment by the sampling tube is achieved due to the favorable internal volume ( approximately 0.4 cm(3) at a length of 470 mm) of the hollow waveguide serving as a miniaturized gas cell. This new method was validated for ethene by thermodesorption-cryofocusing-GC-FID as the reference method. Analytical performance has been compared for standard gas mixtures and for ethene measurements in urban air. Finally, ethene data from a sampling campaign at two alpine sites in Tyrol/Austria are presented.