Intercomparison of measurement techniques for black or elemental carbon under urban background conditions in wintertime: influence of biomass combustion.

A generally accepted method to measure black carbon (BC) or elemental carbon (EC) still does not exist. An earlier study in the Vienna area comparing practically all measurement methods in use in Europe gave comparable BC and EC concentrations under summer conditions (Hitzenberger et al., 2006a). Under summer conditions, Diesel traffic is the major source for EC or BC in Vienna. Under winter conditions, space heating (also with biomass as fuel) is another important source (Caseiro et al., 2007). The present study compares the response of thermal methods (a modified Cachier method, Cachier et al., 1989; a thermal-optical method, Schmid et al., 2001; and two thermal-optical (TOT) methods using Sunset instruments, Birch and Cary, 1996 and Schauer et al., 2003) and optical methods (a light transmission method, Hansen et al., 1984; the integrating sphere method, Hitzenberger et al., 1996; and the multiangle absorption photometer MAAP, Petzold and Schönlinner, 2004). Significant differences were found between the TOT methods on the one hand and all other methods on the other. The TOT methods yielded EC concentrations that were lower by 44 and 17% than the average of all measured concentrations (including the TOT data). The largest discrepancy was found when the contribution of brown carbon (measured with the integrating sphere method) was largest.

Intercomparison of thermal and optical measurement methods for elemental carbon and black carbon at an urban location.

Despite intensive efforts during the past 20 years, no generally accepted standard method exists to measure black carbon (BC) or elemental carbon (EC). Data on BC and EC concentrations are method specific and can differ widely (e.g. Schmid et al., 2001, ten Brink et al., 2004). In this study, a comprehensive set of methods (both optical and thermal) is compared. Measurements were performed under urban background conditions in Vienna, Austria, a city heavily impacted by diesel emissions. Filter and impactor samples were taken during 3 weeks in summer 2002 and analyzed for EC with thermal methods: a modified Cachier method (Cachier et al., 1989), a thermal-optical method (Schmid et al., 2001), and the VDI method (VDI, 1996); for BC with optical methods: a filter transmission method and the integrating sphere method (Hitzenberger et al., 1996); and for total carbon (TC) with a combustion method (Puxbaum and Rendl, 1983). The online methods aethalometer (Hansen et al., 1984) and the multiangle absorption photometer MAAP (Petzold et al., 2002) to measure BC were also used. The average values of BC and EC obtained with the methods agreed within their standard deviations. A conversion table was set up to allow comparisons between data measured elsewhere under urban background conditions (with similar source characteristics) with different instruments. An approach to estimate the absorption coefficient from attenuation data is derived so that existing records of aethalometer data in urban environments may be used to obtain also the absorption coefficients.

Chemometrical exploration of the wet precipitation chemistry from the Austrian Monitoring Network (1988-1999).

The present paper deals with the application of different chemometric methods to an environmental data set derived from the monitoring of wet precipitation in Austria (1988-1999). These methods are: principal component analysis (PCA); projection pursuit (PP); density-based spatial clustering of application with noise (DBSCAN); ordering points to identify the clustering structures (OPTICS); self-organizing maps (SOM), also called the Kohonen network; and the neural gas (NG) network. The aim of the study is to introduce some new approaches into environmetrics and to compare their usefulness with already existing techniques for the classification and interpretation of environmental data. The density-based approaches give information about the occurrence of natural clusters in the studied data set, which, however, do not occur in the case presented here; information about high-density zones (very similar samples) and extreme samples is also obtained. The partitioning techniques (clustering, but also neural gas and Kohonen networks) offer an opportunity to classify the objects of interest into several defined groups, the patterns of ionic concentration of which can be studied in detail. The visual aids, such as the color map and the Kohonen map, for each site are very helpful in understanding the relationships between samples and between samples and variables. All methods, and in particular projection pursuit, give information about samples with extreme characteristics.

Multivariate statistical study of simultaneously monitored cloud water, aerosol and rainwater data from different elevation levels in an Alpine valley (Achenkirch, Tyrol, Austria).

The present paper deals with data interpretation of monitoring of various atmospheric events (cloud water, aerosol and rainwater) at three different elevation levels at Achenkirch profile in an Alpine valley, Tyrol, Austria (Christlumkopf-1758 m, Christlumalm-1280 m and Talboden-930 m a.s.l.) by the use of principal components analysis. From October 1995 to September 1996 sampling sessions for all sites from the profile and for all events were performed for the major ions NH(4)(+), Na(+), K(+), Ca(2+), Mg(2+), Cl(-), NO(3)(-), SO(4)(2-)-44 cases with eight variables for rainwater; 117 cases with eight variables for cloud water samples and 50 cases with seven variables for aerosol (the major ions as in rain- and cloud water but without magnesium) at any of the elevations. The aim of the multivariate statistical treatment was to extract information about latent factors determining the data structure in all of the cases in order to compare and interpret similarities and dissimilarities with respect to the elevation or the type of the atmospheric event. Four latent factors seem to explain over 85% of the total variance for almost all sites and events but the factors have different identification for the different events or sites (e.g. 'anthropogenic', 'crustal', 'neutralization', 'salt'). Thus, a comparison between sites and between events becomes possible. It was found that cloud water and aerosol events are much more similar with respect to data structure (relevant to emission sources or processes of formation) than the same events and rainwater. Further, the upper sites of the profile (Christlumkopf and Christlumalm) also reveal data structure similarity differing from that of the lowest site Talboden.

Bacteria and fungi in aerosols generated by two different types of wastewater treatment plants.

Raw wastewater is a potential carrier of pathogenic microorganisms and may pose a health risk when pathogenic microorganisms become aerosolized during aeration. Two different types of wastewater treatment plants were investigated, and the amounts of cultivable bacteria and fungi were measured in the emitted aerosols. Average concentrations of 17,000 CFU m(-3) of mesophilic, 2,100 CFU m(-3) of TSA-SB bacteria (bacteria associated with certain waterborne virulence factors), 1700 CFU m(-3) of mesophilic and 45 CFU m(-3) of thermotolerant fungi, were found in the aerosol emitted by the aeration tank of the activated sludge plant. In the aerosol of the fixed-film reactor 3000 CFU m(-3) mesophilic and 730CFUm(-3) TSA-SB bacteria, and 180 CFUm(-3) mesophilic and 14 CFU m(-3) thermotolerant fungi were measured. The specific emissions per population equivalent between the two types of treatment plants differed by two orders of magnitude. The microbial flux based on the open water surface area of the two treatment plants was similar. The aerosolization ratios of cultivable bacteria (expressed as CFU m(-3) aerosol/m(-3) wastewater) ranged between 8.4 x 10(-11) and 4.9 x 10(-9). The aerosolization ratio of fungi was one to three orders of magnitude higher and a significant difference between the two types of treatment plants could be observed.

Long-term assessment of the wet precipitation chemistry in Austria (1984-1999).

The aim of the present study was to determine the long-time trends in concentrations and depositions of major ions in wet precipitation samples collected at 11 sampling sites from the Austrian precipitation chemistry network in the period 1984-1999. The analytical results were treated by the use of least square linear regression method. It is shown that a serious decrease of sulfate (between 30% and 60% for the period) and hydrogen ion (between 60% and 102% for the period) concentrations and depositions is achieved at almost all sampling sites and in most of these cases the linear trend proves to be statistically significant. Nitrogen containing ions and base cations do not reveal a distinct trend of changing and in the majority of the sites the linear models are not adequate. In principle, an overall slight concentration and deposition decrease for these major ions is observed (up to 30% for the period of observation) but some substantial exceptions are also found (site Haunsberg or site Lobau). The changes in chloride concentration and deposition, too, do not indicate significant linear trend and, in general, are decreasing for the period of monitoring. In order to give some explanation of the exceptional behaviour of some of the major ions in several sites, an additional comparison with Austrian emission data (sulfur dioxide, nitrogen oxides, ammonium) and with data from five EMEP sites from neighbouring countries is performed. A significant West-East trend of acidity increase is found as well as a good correlation with the emission trends. Therefore, both transboundary and specific local factors could be substantial factors in the wet precipitation chemistry in the region.

A Critical Evaluation of Interlaboratory Data on Total, Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material, NIST SRM 1649a.

Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST "urban dust" Standard Reference Material(®) SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of ((14)C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction). A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) (14)C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and (14)C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic mass balance.

Relationship between release of nitric oxide and CO2 and their dependence on oxidation reduction potential in wastewater treatment.

Nitric oxide (NO) is an intermediate of denitrification process and can be produced by denitrifiers, nitrifiers and other bacteria. In our experiments we measured the dynamic flow of NO depending on oxidation reduction potential (ORP). Different ORP-ranges were related to various carbon loading stages in the wastewater treatment pilot plant. Nitrification and denitrification were achieved by a sequence of aeration and non-aeration periods. Our measurements show that different carbon loading conditions (low feed, balanced and overloaded conditions) did not change the range of the mixing ratio of NO emissions when the aeration conditions like air-flow and temperature were kept constant. Minimum and maximum NO mixing ratios were 34.7 and 91.8 ppbv; 52.3 and 91.3 ppbv; 57.6 and 109 ppbv for low feed, balanced and overloaded conditions, respectively. The curve of the NO graph relied on nitrification/denitrification dynamics. The dependence of NO release on different ORP and CO2-release during the various conditions are shown. Longer aeration times resulted in an increased release of gaseous NO. The net-release of NO g(-1) nitrogen removed was between 0.014% and 0.028%. The NO fluxes to the air were observed between 8.3 and 14.9 mg m(-2) d(-1) NO. The major release occurred during high aeration periods whereas the concentration of dissolved [NOaq] in the wastewater was less than 0.05% of the gaseous release due to very low solubility of the NO.

Trend, seasonal and multivariate modelling study of wet precipitation data from the Austrian Monitoring Network (1990-1997).

The aim of the present study was to analyse the data structure of a large data set from rainwater samples collected during a long-term interval (1990-1997) by the Austrian Precipitation Monitoring Network. Eleven sampling sites from the network were chosen as data sources (chemical concentrations of major ions only) covering various location characteristics (height above sea level, rural and urban sampling positions, Alpine rim and Alpine valley disposition, etc.). The analytical results were treated by the application of already classical environmetric approaches, such as linear regression analysis, time-series analysis and principal components analysis (PCA). For most of the sampling sites, a distinct trend of acidity decrease of the wet precipitation was observed. An overall decrease in sulfate concentration for the whole period and all sites of 3.9% year(-1) (2.0 muequiv. L(-1) year(-1)) was found. The free acidity decrease for most of the sites was between 3.5 and 10.9% year(-1). No significant linear trends were found for nitrate. Base cations either decreased (mean percentage decrease for calcium was 5.4% year(-1) and for magnesium 4.4% year(-1)) or did not show any significant change (sodium, potassium). The overall decrease in ammonium concentration was 2.3% year(-1). Further, some typical "rural" (summer minima and winter maxima) and "urban" (winter minima and spring maxima) seasonal behaviour for the majority of the sites in consideration could be defined, indicating the influence of local emission sources. Several latent factors, named "anthropogenic", "crustal" and "mixed salt", were revealed by the multivariate modelling procedure (PCA) possessing a similar structure for most of the sites. The unavoidable exceptions observed were indications of the influence of sporadic local events (construction and agricultural activities, secondary emission sources, etc.), and an effort was made to explain these exceptions.

Time trends in the concentrations of lead in wet precipitation from rural and urban sites in Austria.

Trend and time series analysis of concentrations of lead in wet precipitation at different rural and urban sampling sites in Austria, collected during intervals of 6-12 years (between 1984 and 1995) is performed. A substantial decrease of the lead concentrations for all sites in consideration is observed similar to observations in Germany, Sweden and North sea and western Atlantic regions. Reductions in rural sites between 60 and 80% in 10 years and around 90% in 10 years in urban areas are found. This trend correlates with the reduction of lead emissions from combustion of gasoline. The seasonal deconvolution model of the data set reveals a typical seasonality with lead concentration peaks in summer and spring for the rural sites and winter peaks for urban sites. The average annual lead concentration in the rural region for 1995 was 1.25 micrograms/l, in the urban region 2.25 micrograms/l.