Leibniz Institute For Tropospharenforschung Tropos

Leipzig, Germany

Leibniz Institute For Tropospharenforschung Tropos

Leipzig, Germany
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Spranger T.,Leibniz Institute For Tropospharenforschung Tropos | Van Pinxteren D.,Leibniz Institute For Tropospharenforschung Tropos | Herrmann H.,Leibniz Institute For Tropospharenforschung Tropos
Environmental Science and Technology | Year: 2017

Organic carbon in atmospheric particles comprises a large fraction of chromatographically unresolved compounds, often referred to as humic-like substances (HULIS), which influence particle properties and impact climate, human health, and ecosystems. To better understand its composition, a two-dimensional (2D) offline method combining size-exclusion (SEC) and reversed-phase liquid chromatography (RP-HPLC) using a new spiked gradient profile is presented. It separates HULIS into 55 fractions of different size and polarity, with estimated ranges of molecular weight and octanol/water partitioning coefficient (log P) from 160-900 g/mol and 0.2-3.3, respectively. The distribution of HULIS within the 2D size versus polarity space is illustrated with heat maps of ultraviolet absorption at 254 nm. It is found to strongly differ in a small example set of samples from a background site near Leipzig, Germany. In winter, the most intense signals were obtained for the largest molecules (>520 g/mol) with low polarity (log P ∼ 1.9), whereas in summer, smaller (225-330 g/mol) and more polar (log P ∼ 0.55) molecules dominate. The method reveals such differences in HULIS composition in a more detailed manner than previously possible and can therefore help to better elucidate the sources of HULIS in different seasons or at different sites. Analyzing Suwannee river fulvic acid as a common HULIS surrogate shows a similar polarity range, but the sizes are clearly larger than those of atmospheric HULIS. © 2017 American Chemical Society.

Gross S.,German Aerospace Center | Freudenthaler V.,Ludwig Maximilians University of Munich | Schepanski K.,Leibniz Institute For Tropospharenforschung Tropos | Toledano C.,University of Valladolid | And 4 more authors.
Atmospheric Chemistry and Physics | Year: 2015

Dual-wavelength Raman and depolarization lidar observations were performed during the Saharan Aerosol Long-range Transport and Aerosol-Cloud interaction Experiment in Barbados in June and July 2013 to characterize the optical properties and vertical distribution of long-range transported Saharan dust after transport across the Atlantic Ocean. Four major dust events were studied during the measurements from 15 June to 13 July 2013 with aerosol optical depths at 532 nm of up to 0.6. The vertical aerosol distribution was characterized by a three-layer structure consisting of the boundary layer, the entrainment or mixing layer and the pure Saharan dust layer. The upper boundary of the pure dust layer reached up to 4.5 km in height. The contribution of the pure dust layer was about half of the total aerosol optical depth at 532 nm. The total dust contribution was about 50-70 % of the total aerosol optical depth at 532 nm. The lidar ratio within the pure dust layer was found to be wavelength independent with mean values of 53 ± 5 sr at 355 nm and 56 ± 7 sr at 532 nm. For the particle linear depolarization ratio, wavelength-independent mean values of 0.26 ± 0.03 at 355 nm and 0.27 ± 0.01 at 532 nm have been found.

Gross S.,German Aerospace Center | Gasteiger J.,Ludwig Maximilians University of Munich | Freudenthaler V.,Ludwig Maximilians University of Munich | Muller T.,Leibniz Institute For Tropospharenforschung Tropos | And 3 more authors.
Atmospheric Chemistry and Physics | Year: 2016

Dual-wavelength lidar measurements with the small lidar system POLIS of the Ludwig-Maximilians-Universität München were performed during the SALTRACE experiment at Barbados in June and July 2013. Based on high-accuracy measurements of the linear depolarization ratio down to about 200 m above ground level, the dust volume fraction and the dust mass concentration within the convective marine boundary layer can be derived. Additional information from radiosonde launches at the ground-based measurement site provide independent information on the convective marine boundary layer height and the meteorological situation within the convective marine boundary layer. We investigate the lidar-derived optical properties, the lidar ratio and the particle linear depolarization ratio at 355 and 532 nm and find mean values of 0.04 (SD 0.03) and 0.05 (SD 0.04) at 355 and 532 nm, respectively, for the particle linear depolarization ratio, and (26 ± 5) sr for the lidar ratio at 355 and 532 nm. For the concentration of dust in the convective marine boundary layer we find that most values were between 20 and 50 μg-3. On most days the dust contribution to total aerosol volume was about 30-40 %. Comparing the dust contribution to the column-integrated sun-photometer measurements we see a correlation between high dust contribution, high total aerosol optical depth and a low Angström exponent, and of low dust contribution with low total aerosol optical depth. © 2016 Author(s).

Van Pinxteren D.,Leibniz Institute For Tropospharenforschung Tropos | Neususs C.,Aalen University of Applied Sciences | Herrmann H.,Leibniz Institute For Tropospharenforschung Tropos
Atmospheric Chemistry and Physics | Year: 2014

Dicarboxylic acids (DCAs) are among the most abundant organic compounds observed in atmospheric aerosol particles and have been extensively studied at many places around the world. The importance of the various primary sources and secondary formation pathways discussed in the literature is often difficult to assess from field studies, though. In the present study, a large data set of size-resolved DCA concentrations from several inland sites in Germany is combined with results from a recently developed approach of statistical back-trajectory analysis and additional data. Principal component analysis is then used to reveal the most important factors governing the abundance of DCAs in different particle size ranges. The two most important sources revealed are (i) photochemical formation during intense radiation days in polluted air masses, likely occurring in the gas phase on short timescales (gasSOA), and (ii) secondary reactions in anthropogenically influenced air masses, likely occurring in the aqueous phase on longer timescales (aqSOA). While the first source strongly impacts DCA concentrations mainly in small and large particles, the second one enhances accumulation mode DCAs and is responsible for the bulk of the observed concentrations. Primary sources were found to be minor (sea salt, soil resuspension) or non-existent (biomass burning, traffic). The results can be regarded as representative for typical central European continental conditions. © Author(s) 2014.

Whalley L.K.,University of Leeds | Stone D.,University of Leeds | George I.J.,University of Leeds | George I.J.,U.S. Environmental Protection Agency | And 6 more authors.
Atmospheric Chemistry and Physics | Year: 2015

The potential for chemistry occurring in cloud droplets to impact atmospheric composition has been known for some time. However, the lack of direct observations and uncertainty in the magnitude of these reactions led to this area being overlooked in most chemistry transport models. Here we present observations from Mt Schmücke, Germany, of the HO2 radical made alongside a suite of cloud measurements. HO2 concentrations were depleted in-cloud by up to 90% with the rate of heterogeneous loss of HO2 to clouds necessary to bring model and measurements into agreement, demonstrating a dependence on droplet surface area and pH. This provides the first observationally derived assessment for the uptake coefficient of HO2 to cloud droplets and was found to be in good agreement with theoretically derived parameterisations. Global model simulations, including this cloud uptake, showed impacts on the oxidising capacity of the troposphere that depended critically on whether the HO2 uptake leads to production of H2O2 or H2O. © Author(s) 2015.

Teich M.,Leibniz Institute For Tropospharenforschung Tropos | Van Pinxteren D.,Leibniz Institute For Tropospharenforschung Tropos | Herrmann H.,Leibniz Institute For Tropospharenforschung Tropos
Electrophoresis | Year: 2014

A hollow-fiber liquid-phase microextraction method was developed to enrich nine nitrophenolic compounds from aqueous extracts of atmospheric aerosol particles. Analysis was performed by CE coupled with ESI MS. The BGE composition was optimized to a 20 mM ammonium acetate buffer at pH 9.7 containing 15% methanol v/v. Several extraction parameters (composition of organic liquid membrane, pH of acceptor phase, salting-out effect, extraction time) were investigated for their effect on the analyte recoveries. The donor phase consisted of a 1.8 mL sample solution kept at pH 2 while the acceptor phase was a 15 μL 100 mM aqueous ammonia solution. Dihexyl ether served as supported liquid membrane. Low detection limits in the range of nanomole per liter were achieved. Recoveries of aqueous standard solutions were found to be between 11 and 90% with enrichment factors between 10 and 100. Interday and intraday repeatabilities were in an acceptable range for most compounds (6-15% and 7-10%, respectively) but somewhat higher for 4-nitrocatechol (59 and 48%) and 2-nitrophenol (17 and 35%). The developed method was found to be competitive with more established method and was successfully applied to samples of atmospheric particulate matter from field experiments. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iinuma Y.,Leibniz Institute For Tropospharenforschung Tropos | Keywood M.,CSIRO | Herrmann H.,Leibniz Institute For Tropospharenforschung Tropos
Atmospheric Environment | Year: 2016

Detailed chemical characterisation was performed for wintertime and summertime PM10 samples collected in Melbourne, Australia. The samples were analysed for marker compounds of biomass burning and biogenic secondary organic aerosol (SOA). The chemical analysis showed that the site was significantly influenced by the emissions from wintertime domestic wood combustion and summertime bushfires. Monosaccharide anhydrides were major primary biomass burning marker compounds found in the samples with the average concentrations of 439, 191, 57 and 3630 ngm-3 for winter 2004, winter 2005, summer 2005 and summer 2006, respectively. The highest concentration was determined during the summer 2006 bushfire season with the concentration of 15,400 ngm-3. Biomass burning originating SOA compounds detected in the samples include substituted nitrophenols, mainly 4-nitrocatechol (Mr 155), methyl-nitrocatechols (Mr 169) and dimethyl-nitrocatechols (Mr 183) with the sum concentrations as high as 115 ngm-3 for the wintertime samples and 770 ngm-3 for the bushfire influenced samples. In addition to this, elevated levels of biogenic SOA marker compounds were determined in the summertime samples influence by bushfire smoke. These marker compounds can be categorised into carboxylic acid marker compounds and heteroatomic organic acids containing nitrogen and sulfur. Carboxylic acid marker compounds can be largely attributed to oxidation products originating from 1,8-cineole, α-pinene and β-pinene that are main constituents of eucalyptus VOC emissions. Among those, diaterpenylic acid, terpenylic acid and daterebic acid were found at elevated levels in the bushfire influenced samples. Heteroatomic monoterpene SOA marker compounds (Mr 295, C10H17NO7S) were detected during both winter and summer periods. Especially high levels of these compounds were determined in the severe bushfire samples from summer 2006. Based on the results obtained from the chemical analysis and a macro tracer method, we estimated that 1,8-cineole SOA alone contributed up to 3.5% of secondary organic carbon mass during the bushfire period in 2006. It is likely that biogenic VOC oxidation can be an important source of biomass burning organic aerosol mass. © 2015 Elsevier Ltd.

Spindler G.,Leibniz Institute For Tropospharenforschung Tropos | Gruner A.,Leibniz Institute For Tropospharenforschung Tropos | Muller K.,Leibniz Institute For Tropospharenforschung Tropos | Schlimper S.,Deutsche WetterSchutz GmbH | Herrmann H.,Leibniz Institute For Tropospharenforschung Tropos
Journal of Atmospheric Chemistry | Year: 2013

Size-segregated high-volume (HV) quartz filter samples were collected daily at the Melpitz rural site in Germany for PM10 (November 1992 until April 2012), and for PM2.5 and PM1 (January 2003 until April 2012, PM1 sampled every sixth day). The samples were analysed for mass concentration (gravimetrically), water-soluble ions (ion-chromatography) and since 2003 for organic carbon (OC) and elemental carbon (EC) (thermography). The long-term measurements first show a decreasing trend for PM10 (1993-2000) followed by a second period (2001-2011) with a mean mass concentration of about 22.4 μgm-3 and an inter-annual variation of about ± 2.9 μgm-3 (13% fluctuation margin). The absolute sulphate and calcium concentration (for the full period), as well as the EC concentration (time after 2003) decrease by about 50, 75 and 30% for PM10, respectively. The nitrate concentration remains constant all the time. For the daily objective weather type classification (OWTC, 1993-2002) the highest PM10 concentration was found for South-East (SE) and the lowest for North-West (NW) wind direction with 44 and 24 μgm-3, respectively. These concentrations decrease for 2003-2011 in comparison to 1993-2002 by about 21% and 26%, respectively. The highest PM10, PM2.5 and PM1 concentrations (2003-2011) were found for SE and the lowest for NW wind direction with about 34 and 17 μgm-3 (PM10), 28 and 19 μgm-3 (PM2.5) and 22 and 11 μgm-3 (PM1), respectively. The relative content of sulphate, OC and EC was the highest for SE wind direction. A differentiation into four categories for winter (Wi) and summer (Su) and air mass inflow from West (W) and East (E) was carried out. The highest PM concentrations were observed for WiE with the highest inter-annual fluctuation. In this category sulphate contents are largest. The lowest concentrations where found for SuW. The means for WiE show the strongest relative decreases, e.g. in PM10 sulphate (1993-2011) and EC (2003-2011) by about 60% and 40%, respectively. Nitrate is an indicator for NOx motor-car emissions. It shows a typical variation with maximum values in the middle of the week, especially for air mass inflow from West. In contrast, chloride mostly originating from sea spray doesn't show such a concentration pattern. The PM2.5/PM10 as well the PM1/PM 10-ratio have the highest median (0.878 and 0.654) during WiE and the lowest (0.718 and 0.578) during SuW, respectively. For the ratio PM 2.5/PM10 a slightly increasing trend was found (about 0.71 and 0.83 for 1995 and 2011, respectively). The increase is stronger in summer than in winter. © 2013 Springer Science+Business Media Dordrecht.

Kahnt A.,Leibniz Institute For Tropospharenforschung Tropos | Kahnt A.,University of Antwerp | Iinuma Y.,Leibniz Institute For Tropospharenforschung Tropos | Mutzel A.,Leibniz Institute For Tropospharenforschung Tropos | And 3 more authors.
Atmospheric Chemistry and Physics | Year: 2014

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS2 and MS3 fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m/z 201, C 9H14O5 and m/z215, C10H 16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m/z 201 and 215 compounds were tentatively identified as a C9-and C10-carbonyl- dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives. © Author(s) 2014.

Van Pinxteren M.,Leibniz Institute For Tropospharenforschung Tropos | Herrmann H.,Leibniz Institute For Tropospharenforschung Tropos
Atmospheric Chemistry and Physics | Year: 2013

An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6- Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD < 10%), sensitivity (detection limits in the low ng L-1 range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng L -1 (GLY) and 196 ng L-1 (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng m-3) and MGLY (average concentration 0.15 ng m-3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere. © 2013 Author(s).

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