Andreas Limbeck

Seasonal trends and possible sources of brown carbon based on 2-year aerosol measurements at six sites in Europe

Brown carbon is a ubiquitous and unidentified component of organic aerosol which has recently come into the forefront of atmospheric research. This component is strongly linked to the class of humic-like substances (HULIS) in aerosol whose ultimate origin is still being debated. Using a simplified spectroscopic method the concentrations of brown carbon have been determined in aqueous extracts of fine aerosol collected during the CARBOSOL project. On the basis of the results of 2-year measurements of several aerosol constituents at six European sites, possible sources of brown carbon are inferred. Biomass burning ( possibly domestic wood burning) is shown to be a major source of brown carbon in winter. At elevated sites in spring, smoke from agricultural fires may be an additional source. Direct comparison of measured brown carbon concentrations with HULIS determined by an independent method reveals that the two quantities correlate well at low-elevation sites throughout the year. At high-elevation sites the correlation is still high for winter but becomes markedly lower in summer, implying different sources and/or atmospheric sinks of brown carbon and HULIS. The results shed some light on the relationships between atmospheric brown carbon and HULIS, two ill-defined and overlapping components of organic aerosol.

Relationship between Cation Segregation and the Electrochemical Oxygen Reduction Kinetics of La0.6Sr0.4CoO3−δ Thin Film Electrodes

Pulsed laser deposited La 0.6 Sr 0.4 CoO 3―δ (LSC) thin film electrodes on yttria stabilized zirconia (YSZ) single crystals were investigated by impedance spectroscopy, time of flight secondary ion mass spectrometry (ToF-SIMS) and inductively coupled plasma optical emission spectrometry (ICP-OES). Effects caused by different film deposition temperatures, thermal annealing and chemical etching were studied. Correlations between changes in electrode polarization resistance of oxygen reduction and surface composition were found. At high deposition temperatures and after thermal annealing an inhomogeneous cation distribution was detected in the surface-near region, most manifest in a significant Sr enrichment at the surface. An activating effect of chemical etching of LSC is described, which can lower the polarization resistance by orders of magnitude. Chemistry behind this activation and thermal degradation was analyzed by ToF-SIMS and ICP-OES measurements of in-situ etched LSC films. The latter allow quantitative depth resolved compositional analysis with nominally sub nm resolution. High resolution scanning electron microscopy images illustrate the accompanying changes in surface morphology. All measurements suggest that stoichiometric LSC surfaces intrinsically exhibit very high activity towards oxygen reduction.

Determination of Pt, Pd and Rh by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) in size-classified urban aerosol samples

Pt, Pd and Rh concentration levels related to particle size distribution were measured in Viennese aerosol. The urban aerosol was studied over a period of 1 month during summer 2002 in a heavy traffic area. A 6-stage cascade impactor collected classified particles with aerodynamic equivalent diameter (aed) <10 µm. Total suspended particulate matter (aed <30 µm) was assessed by filtering air (open face sampling head). The analysis of Pt, Pd and Rh in aerosol samples required a different strategy for each element to obtain accurate results and maximum sensitivity. Sample preparation was carried out by microwave-assisted acid digestion. For the determination of Pd an anion-exchange procedure was implemented. The digested samples were measured by ICP-SFMS in combination with ultrasonic nebulization and membrane desolvation, utilizing the high-resolution capabilities of this instrument for the determination of Rh. Pt and Pd were quantified by isotope dilution (IDMS), Rh by external calibration. Excellent detection limits of 0.07, 0.06 and 0.05 pg m−3 (impactor substrates) and 0.18, 0.22, 0.14 pg m−3 (open face sampling head substrates) for Pd, Pt and Rh, respectively, could be achieved. Since platinum group elements (PGE) are emitted from car catalysts as a result of mechanical processes, Pt, Pd and Rh were mainly found in the coarse fraction of urban aerosol. Summing up the concentrations assessed for the impactor stages (aed <10 µm) revealed a weekly average of 4.3 ± 1.7, 2.6 ± 0.6 and 0.4 ± 0.1 pg m−3 for Pt, Pd and Rh respectively. Concentration levels of samples collected with the open face sampling head (aed <30 µm) over the period of one week were significantly higher with average values of 38.1 ± 6.3, 14.4 ± 3.1 and 6.6 ± 2.4 pg m−3. Moreover, the presence of a collective of small particles containing the three investigated PGE was shown. Investigation of the impactor samples revealed an analogue size distribution for Pt, Rh and Pd with a maximum at 1–2.15 µm aed. These particles are toxicological relevant, as they penetrate deeply in human lungs (particles of 0.1–2.5 µm aed are deposited in the lung alveoli).

Recent advances in quantitative LA-ICP-MS analysis: challenges and solutions in the life sciences and environmental chemistry

Laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) is a widely accepted method for direct sampling of solid materials for trace elemental analysis. The number of reported applications is high and the application range is broad; besides geochemistry, LA-ICP-MS is mostly used in environmental chemistry and the life sciences. This review focuses on the application of LA-ICP-MS for quantification of trace elements in environmental, biological, and medical samples. The fundamental problems of LA-ICP-MS, such as sample-dependent ablation behavior and elemental fractionation, can be even more pronounced in environmental and life science applications as a result of the large variety of sample types and conditions. Besides variations in composition, the range of available sample states is highly diverse, including powders (e.g., soil samples, fly ash), hard tissues (e.g., bones, teeth), soft tissues (e.g., plants, tissue thin-cuts), or liquid samples (e.g., whole blood). Within this article, quantification approaches that have been proposed in the past are critically discussed and compared regarding the results obtained in the applications described. Although a large variety of sample types is discussed within this article, the quantification approaches used are similar for many analytical questions and have only been adapted to the specific questions. Nevertheless, none of them has proven to be a universally applicable method.

Comparative analysis of the Trichoderma reesei transcriptome during growth on the cellulase inducing substrates wheat straw and lactose.

BackgroundRenewable lignocellulosic biomass is an advantageous resource for the production of second generation biofuels and other biorefinery products. In Middle Europe, wheat straw is one of the most abundant low-cost sources of lignocellulosic biomass. For its efficient use, an efficient mix of cellulases and hemicellulases is required. In this paper, we investigated how cellulase production by T. reesei on wheat straw compares to that on lactose, the only soluble and also cheap inducing carbon source for enzyme production.ResultsWe have examined and compared the transcriptome of T. reesei growing on wheat straw and lactose as carbon sources under otherwise similar conditions. Gene expression on wheat straw exceeded that on lactose, and 1619 genes were found to be only induced on wheat straw but not on lactose. They comprised 30% of the CAZome, but were also enriched in genes associated with phospholipid metabolism, DNA synthesis and repair, iron homeostatis and autophagy. Two thirds of the CAZome was expressed both on wheat straw as well as on lactose, but 60% of it at least >2-fold higher on the former. Major wheat straw specific genes comprised xylanases, chitinases and mannosidases. Interestingly, the latter two CAZyme families were significantly higher expressed in a strain in which xyr1 encoding the major regulator of cellulase and hemicellulase biosynthesis is non-functional.ConclusionsOur data reveal several major differences in the transcriptome between wheat straw and lactose which may be related to the higher enzyme formation on the former and their further investigation could lead to the development of methods for increasing enzyme production on lactose.

Dependence of in-cloud scavenging of polar organic aerosol compounds on the water solubility

In spring 1997 at the Sonnblick Observatory, located at 3106m elevation in the Austrian Alps, interstitial aerosol and cloud water samples were simultaneously collected in supercooled convective clouds. These samples were analyzed for their polar organic composition using a newly developed analytical method that allows the simultaneous determination of dicarboxylic acids, monocarboxylic acids, and other polar organic constituents. Using the obtained data set, in-cloud scavenging efficiencies (e) for individual polar organic compounds were calculated. For the different organic substances, scavenging efficiencies ranged from 0.16 to 0.98, compared with sulfate, which exhibited an average scavenging efficiency of 0.94. For dicarboxylic acids, scavenging efficiencies (average of about 0.8) were of the same order as for sulfate. Distinctly lower values (average of about 0.6) were achieved for polar aromatic compounds like phthalic acid or diisobutylphenol. The lowest scavenging efficiencies (average about 0.4) were found for alcohols and monocarboxylic acids. Thus we found in the Sonnblick cloud experiment that more polar organic aerosol constituents are more efficiently scavenged into cloud droplets than less polar compounds. In addition, the scavenging efficiencies exhibited a dependence on the solubilities of the examined compounds. For highly water soluble compounds (1–1000 g L−1) a decrease of the water solubility for an individual compound leads to a decrease in the scavenging efficiency for this compound. For “poorly soluble” substances with water solubilities below l g L−1, a near-constant value for the scavenging efficiency was found, indicating that their scavenging behavior is then dominated by the scavenging of the bulk noncarbonate carbon independent of the physical and chemical properties of the individual substances.

ETAAS determination of palladium in environmental samples with on-line preconcentration and matrix separation

A flow injection procedure with ETAAS detection for the on-line matrix separation and preconcentration of palladium in environmental samples such as airborne particulate matter and road dust was developed. The selective enrichment of palladium was performed on a C18 micro column which has been reversibly loaded with the complexing agent N,N-diethyl-N′-benzoylthiourea. The formed palladium complex was eluted with ethanol and directly introduced into the graphite furnace. With the use of a 1.57 ml sample loop a limit of detection of 23 ng l−1 and a limit of quantification of 39 ng l−1 were obtained for the determination of palladium, with a relative standard deviation being not more than 3.9%. The method including the developed digestion procedure has been evaluated using the certified reference material BCR-723 (road dust). Finally the procedure was applied for the analysis of aerosol samples from the urban site Vienna.

Recent developments in assessment of bio-accessible trace metal fractions in airborne particulate matter: A review

In the last years a great deal of research has been focused on the determination of harmful trace metals such as Cd, Co, Cr, Cu, Ni or Pb in airborne particulate matter (APM). However, the commonly applied determination of total element concentrations in APM provides only an upper-end estimate of potential metal toxicity. For improved risk assessment it is important to determine bio-accessible concentrations instead of total metal contents. The present review gives an overview of analytical procedures reported for measurement of bio-accessible trace metal fractions in APM. The different approaches developed for extraction of soluble trace metals in APM are summarized. Furthermore the analytical techniques applied for accurate determination of dissolved trace metals in the presence of complex sample matrix are presented. Finally a compilation of published results for bio-accessible trace metals in APM is included.

Black carbon and other species at a high‐elevation European site (Mount Sonnblick, 3106 m, Austria): Concentrations and scavenging efficiencies

During a recent measurement project, several intensive campaigns were performed on Mount Sonnblick (3106 m above sea level) in the Austrian central range of the Alps. Cloud water and interstitial aerosol samples were obtained from supercooled clouds by using a specially designed cloud water sampler [Kruisz et al., 1993]. The samples were analyzed for black carbon (BC) by an optical technique (integrating sphere [Hitzenberger et al. 1996]) using liquid samples, for major inorganic ions by ion chromatography and for total carbon (TC) by a combusion method. During the fall campaign of 1996, cloud water BC concentrations ranged from 0.45 to 3.64 μg/mL (average concentration 0.85 μg/mL). During the spring 1997 campaign, cloud water BC concentrations ranged from 0.55 to 2.95 μg/mL (average concentration 1.07 μg/mL). The dominant ion in cloud water was SO42− with concentrations from 0.36 to 86.5 μg/mL (average 6.83 μg/mL) in fall 1996 and 0.31–15.4 μg/mL (average 3.06 μg/mL) in spring 1997. In the individual samples, the BC/SO42− ratio ranged from 0.036 to 1.2 (average 0.316) in fall 1996 and 0.036 to 2.04 (average 0.79) in spring 1997. The extreme values were usually confined to short periods within one cloud event. Scavenging efficiencies e were calculated by using cloud water and interstitial aerosol concentrations from samples obtained simultaneously with the cloud water sampler for the 1997 campaign. For BC, eBC = 0.74 (±0.19) was found, while the values for SO42− and TC were eSO4 = 0.91 (±0.08) and eTC = 0.57 (±0.21), respectively. The findings of an earlier study [Kasper-Giebl et al., 2000], where eSO4 depended on the liquid water content, were confirmed here for all the three substances.

Surface chemistry of La0.6Sr0.4CoO3−δ thin films and its impact on the oxygen surface exchange resistance

The surface composition of dense La0.6Sr0.4CoO3−δ (LSC) thin film model electrodes, deposited by pulsed laser deposition at 600 °C on yttria-stabilized zirconia (100) electrolytes, was investigated by low-energy ion scattering (LEIS) and time resolved inductively coupled plasma mass spectrometry (ICP-MS). Results obtained by both methods agree qualitatively and quantitatively and provide a comprehensive picture of the surface composition and cation diffusion kinetics of LSC. The measurements revealed that freshly prepared LSC thin films already show a Sr-rich and Co-poor termination layer (80% Sr surface coverage). This Sr-rich surface layer was proven to be an equilibrium property of LSC as it forms again at elevated temperatures after removal. The kinetics of this surface reconstruction is surprisingly fast (<1 h at 550 °C) and indicates high Sr mobility in LSC. Electrochemical Impedance Spectroscopy (EIS) measurements at 400 °C revealed the detrimental effect of this surface layer on the oxygen surface exchange and suggest that higher Co concentrations in the termination layer facilitate the oxygen exchange reaction.