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Biomedical subjects

Ulrich Pöschl

Publications and source records attributed to Ulrich Pöschl.

9 recordsLinked to original sources

Atmospheric aerosols: composition, transformation, climate and health effects.

Aerosols are of central importance for atmospheric chemistry and physics, the biosphere, climate, and public health. The airborne solid and liquid particles in the nanometer to micrometer size range influence the energy balance of the Earth, the hydrological cycle, atmospheric circulation, and the abundance of greenhouse and reactive trace gases. Moreover, they play important roles in the reproduction of biological organisms and can cause or enhance diseases. The primary parameters that determine the environmental and health effects of aerosol particles are their concentration, size, structure, and chemical composition. These parameters, however, are spatially and temporally highly variable. The quantification and identification of biological particles and carbonaceous components of fine particulate matter in the air (organic compounds and black or elemental carbon, respectively) represent demanding analytical challenges. This Review outlines the current state of knowledge, major open questions, and research perspectives on the properties and interactions of atmospheric aerosols and their effects on climate and human health.

Aerosols↗

Protein nitration by polluted air.

The effects of air pollution on allergic diseases are not yetwell-understood. Here, we show that proteins, in particular birch pollen proteins including the allergen Bet v 1, are efficiently nitrated by polluted air. This posttranslational modification of proteins is likely to trigger immune reactions and provides a molecular rationale for the promotion of allergies bytraffic-related air pollution. Enzyme immunoassays have been used to determine equivalent degrees of nitration (EDN) for protein samples exposed to urban outdoor air and synthetic gas mixtures. The observed rates of nitration were governed by the abundance of nitrogen oxides and ozone, and concentration levels typical for summer smog conditions led to substantial nitration within a few hours to days (EDN up to 20%). Moreover, nitrated proteins were detected in urban road dust, window dust, and fine air particulate matter (EDN up to 0.1%).

Air Pollutants↗

Analysis of nitrated polycyclic aromatic hydrocarbons by liquid chromatography with fluorescence and mass spectrometry detection: air particulate matter, soot, and reaction product studies.

Polycyclic aromatic hydrocarbons (PAH) and their nitrated derivatives (nitro-PAH) are environmental pollutants which pose a threat to human health even at low concentration levels. In this study, efficient analytical methods for the analysis of nitro-PAH and PAH (extraction, clean-up, chromatographic separation, and spectrometric detection) have been developed, characterized, and applied to aerosol samples. The separation and quantification of 12 nitro-PAH was carried out by reversed-phase high performance liquid chromatography (HPLC), on-line reduction, and fluorescence detection. The detection limits were in the range of 0.03-0.5 microg L(-1) (6-100 pg in the investigated sample aliquots), and the recovery rates from soot samples were 70-90%. Nitro-PAH and PAH concentrations have been determined for different types of soot and for urban, rural, and alpine fine air particulate matter (PM2.5). For the first time, trace amounts of nitro-PAH have been detected in a high-alpine clean air environment. The on-line reduction and fluorescence technique has been complemented by atmospheric pressure chemical ionization time-of-flight mass spectrometry (APCI-TOF-MS). The MS detection allowed the analysis of partially nitrated and oxygenated PAH in laboratory studies of the heterogeneous reaction of PAH on soot and glass fiber substrates with gaseous nitrogen oxides and ozone. It led to the tentative identification of a previously unknown nitrated derivative of the particularly toxic PAH benzo[ a]pyrene (BaP-nitroquinone), and provides the first experimental evidence that PAH-nitroquinones can be formed by reaction of PAH with atmospheric photooxidants.

Journal Article↗

Polycyclic aromatic hydrocarbons in urban air particulate matter: decadal and seasonal trends, chemical degradation, and sampling artifacts.

Aerosol filter samples collected at a major urban traffic junction (LKP) and at a suburban residential location (IWC) in the metropolitan area of Munich (Germany) throughout the years 2001 and 2002 have been analyzed for 12 of the 16 EPA priority polycyclic aromatic hydrocarbon (PAH) pollutants by liquid chromatography with fluorescence detection. The mean mass concentration of the sum of all investigated PAH in the sampled air at LKP (1.9-5.0 ng m(-3)) was roughly two times higher than at IWC (0.8-2.9 ng m(-3)), and at both locations it was about 2-3 times higher in winter (heating season) than in summer and spring or autumn. Comparisons with earlier measurement campaigns indicate a steep decrease of PAH abundance by almost an order of magnitude from 1980 to 1993 and a much slower decrease since then. Distinctly different seasonal trends and short-term fluctuations have been observed for semivolatile 3- and 4-ring PAH and for particle-bound 5- and 6-ring PAH. Based on systematic correlation analyses with a wide range of air quality parameters, most of the differences can be attributed to not only varying emissions but also chemical reactions with atmospheric oxidants which were found to play an important role. The results of denuder experiments prove that substantial degradation of the particularly toxic tracer benzo[a]pyrene and of the other investigated 5- and 6-ring PAH can occur during filter sampling and on airborne particles (formation of oxygenated and nitrated derivatives). Filter reaction artifacts are shown to lead to an underestimation of the actual PAH content of urban air particulate matter by up to 100% of the measurement value or more, with a near-linear dependence on ozone volume mixing ratio. The role and applicability of ozone as a tracer of atmospheric oxidizing capacity for particle-bound PAH is discussed and confirmed by comparison with earlier investigations and by complementary laboratory experiments (reaction kinetics and product studies).

Air Pollutants↗

The diesel exhaust component pyrene induces expression of IL-8 but not of eotaxin.

Environmental pollutants can influence the expression of immunoregulatory molecules and, in this way, promote allergies. The local synthesis of proinflammatory chemokines is an important aspect in the development of allergic airway inflammation. We have characterized the influence of pyrene, a polycyclic aromatic hydrocarbon (PAH) contained, for example, in diesel exhaust particles (DEP), on transcription and secretion of the chemokines interleukin-8 (IL-8) and eotaxin. Reporter genes under control of the respective promoters were tested in the human cell lines A549 and HeLa, mRNA production was assayed in A549 cells and protein production was measured by ELISA in cell supernatants from primary human fibroblasts. Pyrene content of cell supernatants was measured by analytical HPLC. Promoter activity, mRNA production and protein expression of IL-8 were increased by pyrene. The activating effect in reporter gene studies was abolished by mutating either an NF-kappaB or an AP-1 binding site in the IL-8 promoter. In contrast, pyrene showed no effect on transcription from the eotaxin promoter, despite the important role of this chemokine in asthma. Our data show that pyrene has specific effects on chemokine synthesis, which are not restricted to mediators primarily associated with atopic diseases. Pyrene also affected cells not derived from lung tissue, which suggests a broader immunoregulatory influence for this pollutant.

Air Pollutants↗

Enzyme immunoassays for the investigation of protein nitration by air pollutants.

Two enzyme immunoassays have been developed, characterised, and applied to investigate protein nitration in birch pollen extract (BPE) and bovine serum albumin (BSA) samples exposed to air pollutants. The monoclonal antibody CAY-189542 against nitrotyrosine (raised against peroxynitrite-treated keyhole limpet hemocyanine) was characterised in an indirect competitive assay (affinity and cross-reactivities) and applied in a new one-sided enzyme immunoassay for nitrated proteins. The one-sided assay was calibrated against a nitrated BSA standard with an average of 14 nitrotyrosine residues per molecule (nitro-(14)-BSA; detection limit 8.3 pmol L(-1)), and the sensitivity of the test was found to be significantly enhanced by a multivalent binding mode of the monoclonal antibody (bonus effect of multivalency). The same antibody and a polyclonal antibody against Bet v 1, the most prominent birch pollen allergen, were used in a new sandwich immunoassay for specific determination of nitrated Bet v 1. This assay was calibrated against a nitrated Bet v 1 standard with an average of 3 nitrotyrosine residues per molecule (nitro-(3)-Bet v 1; detection limit 0.2 nmol L(-1)). Bet v 1 and BSA exposed to polluted urban outdoor air and to synthetic gas mixtures containing NO2 and O3 at atmospherically relevant concentration levels were found to be efficiently nitrated within hours to days. Pronounced correlations of nitro-(14)-BSA equivalent concentrations with exposure time and with nitro-(3)-Bet v 1 equivalent concentrations in nitrated BPE samples were observed. Test experiments indicated that the efficiency of protein nitration was strongly enhanced by reactive species formed upon interaction of NO2 with O3 and H2O (e.g. NO3 and HNO3). Potential implications of protein nitration by air pollutants are outlined and discussed.

Air Pollutants↗

Formation and decomposition of hazardous chemical components contained in atmospheric aerosol particles.

Air particulate matter contains a wide range of substances, some of which pose a threat to human health. Chemical reactions occurring on aerosol particles in the atmosphere can transform hazardous components and increase or decrease their potential for adverse health effects. Especially organic compounds react readily with atmospheric oxidants, and since fine aerosol particles have a high surface-to-volume ratio, their chemical composition can be efficiently changed by interaction with trace gases such as ozone and nitrogen oxides. In this paper the concepts required to understand and describe the formation and decomposition of hazardous chemical components contained in atmospheric aerosol particles are outlined. The processes at work on a molecular level in the chemical transformation of atmospheric particle components are illustrated for soot and polycyclic aromatic compounds (PACs), in particular for benzo[a]pyrene (BaP) which is one of the most prominent hazardous pollutants in the class of polycyclic aromatic hydrocarbons (PAHs). Recent results on the reaction kinetics and mechanisms of BaP degradation by ozone and nitrogen dioxide are presented. These results indicate faster degradation by atmospheric oxidants than previously estimated, which implies a higher potential for sampling artifacts and underestimation of the actual atmospheric abundance of BaP and other PAHs. Thus human exposure close to the sources of these compounds such as busy roadways may be significantly higher than previously assumed.

Aerosols↗

Liquid- and gas-phase nitration of bovine serum albumin studied by LC-MS and LC-MS/MS using monolithic columns.

Post-translational nitration of proteins was analyzed by capillary reversed-phase high-performance liquid chromatography (RP-HPLC) on-line interfaced to electrospray ionization mass spectrometry (ESI--MS) or tandem mass spectrometry (ESI--MS/MS). Both methods were compared using a tryptic digest of bovine serum albumin (BSA) and yielded sequence coverages of 95% and 33% with RP-HPLC--ESI--MS and RP-HPLC--ESI--MS/MS, respectively. At least 95% of the tyrosines were covered by the former method, whereas the latter method only detected less than 50% of the tyrosine-containing peptides. Upon liquid-phase nitration of BSA in aqueous solution using an excess of tetranitromethane, at least 16 of the 20 tyrosine residues were found to be nitrated. After exposure of solid BSA samples to gaseous nitrogen dioxide and ozone at atmospherically relevant concentration levels, only 3 nitrated peptides were detected. By use of such a model system, RP-HPLC--ESI--MS proved to be a rapid and highly efficient method for the comprehensive and quantitative detection of protein nitration.

Amino Acid Sequence↗