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- ItemTreatment of non-ideality in the SPACCIM multiphase model - Part 1: Model development(München : European Geopyhsical Union, 2016) Rusumdar, A.J.; Wolke, R.; Tilgner, A.; Herrmann, H.Ambient tropospheric deliquesced particles generally comprise a complex mixture of electrolytes, organic compounds, and water. Dynamic modeling of physical and chemical processes in this complex matrix is challenging. Thus, up-to-date multiphase chemistry models generally do not consider non-ideal solution effects. Therefore, the present study was aimed at presenting further development of the SPACCIM (Spectral Aerosol Cloud Chemistry Interaction Model) through treatment of solution non-ideality, which has not been considered before. The present paper firstly describes the model developments including (i) the implementation of solution non-ideality in aqueous-phase reaction kinetics in the SPACCIM framework, (ii) the advancements in the coupling scheme of microphysics and multiphase chemistry and (iii) the required adjustments of the numerical schemes, especially in the sparse linear solver and the calculation of the Jacobian. Secondly, results of sensitivity investigations are outlined, aiming at the evaluation of different activity coefficient modules and the examination of the contributions of different intermolecular forces to the overall activity coefficients. Finally, first results obtained with the new model framework are presented. The SPACCIM parcel model was developed and, so far, applied for the description of aerosol–cloud interactions. To advance SPACCIM also for modeling physical and chemical processes in deliquesced particles, the solution non-ideality has to be taken into account by utilizing activities in reaction terms instead of aqueous concentrations. The main goal of the extended approach was to provide appropriate activity coefficients for solved species. Therefore, an activity coefficient module was incorporated into the kinetic model framework of SPACCIM. Based on an intercomparison of different activity coefficient models and the comparison with experimental data, the AIOMFAC approach was implemented and extended by additional interaction parameters from the literature for mixed organic–inorganic systems. Moreover, the performance and the capability of the applied activity coefficient module were evaluated by means of water activity measurements, literature data and results of other activity coefficient models. Comprehensive comparison studies showed that the SpactMod (SPACCIM activity coefficient module) is valuable for predicting the thermodynamic behavior of complex mixtures of multicomponent atmospheric aerosol particles. First simulations with a detailed chemical mechanism have demonstrated the applicability of SPACCIM-SpactMod. The simulations indicate that the treatment of solution non-ideality might be needed for modeling multiphase chemistry processes in deliquesced particles. The modeled activity coefficients imply that chemical reaction fluxes of chemical processes in deliquesced particles can be both decreased and increased depending on the particular species involved in the reactions. For key ions, activity coefficients on the order of 0.1–0.8 and a strong dependency on the charge state as well as the RH conditions are modeled, implying a lowered chemical processing of ions in concentrated solutions. In contrast, modeled activity coefficients of organic compounds are in some cases larger than 1 under deliquesced particle conditions and suggest the possibility of an increased chemical processing of organic compounds. Moreover, the model runs have shown noticeable differences in the pH values calculated with and without consideration of solution non-ideality. On average, the predicted pH values of the simulations considering solution non-ideality are −0.27 and −0.44 pH units lower under 90 and 70 % RH conditions, respectively. More comprehensive results of detailed SPACCIM-SpactMod studies on the multiphase processing in organic–inorganic mixtures of deliquesced particles are described in a companion paper.
- ItemMeasurements of PM10 ions and trace gases with the online system MARGA at the research station Melpitz in Germany – A five-year study(Dordrecht : Springer, 2017) Stieger, B.; Spindler, G.; Fahlbusch, B.; Müller, K.; Grüner, A.; Poulain, L.; Thöni, L.; Seitler, E.; Wallasch, M.; Herrmann, H.An hourly quantification of inorganic water-soluble PM10 ions and corresponding trace gases was performed using the Monitor for AeRosols and Gases in ambient Air (MARGA) at the TROPOS research site in Melpitz, Germany. The data availability amounts to over 80% for the five-year measurement period from 2010 to 2014. Comparisons were performed for the evaluation of the MARGA, resulting in coefficients of determinations (slopes) of 0.91 (0.90) for the measurements against the SO2 gas monitor, 0.84 (0.88), 0.79 (1.39), 0.85 (1.20) for the ACSM NO3 −, SO4 2− and NH4 + measurements, respectively, and 0.85 (0.65), 0.88 (0.68), 0.91 (0.83), 0.86 (0.82) for the filter measurements of Cl−, NO3 −, SO4 2− and NH4 +, respectively. A HONO comparison with a batch denuder shows large scatter (R2 = 0.41). The MARGA HNO3 is underestimated compared to a batch and coated denuder with shorter inlets (slopes of 0.16 and 0.08, respectively). Less NH3 was observed in coated denuders for high ambient concentrations. Long-time measurements show clear daily and seasonal variabilities. Potential Source Contribution Function (PSCF) analysis indicates the emission area of particulate ions Cl−, NO3 −, SO4 2−, NH4 +, K+ and gaseous SO2 to lie in eastern European countries, predominantly in wintertime. Coarse mode sea salt particles are transported from the North Sea to Melpitz. The particles at Melpitz are nearly neutralised with a mean molar ratio of 0.90 for the five-year study. A slight increase of the neutralization ratio over the last three years indicates a stronger decrease of the anthropogenically emitted NO3 − and SO4 2− compared to NH4 +.
- ItemModeling the multiphase processing of an urban and a rural air mass with COSMO-MUSCAT(Amsterdam : Elsevier, 2014) Schrödner, R.; Tilgner, A.; Wolke, R.; Herrmann, H.A reduced version of the complex aqueous phase mechanism CAPRAM3.0i (C3.0RED) was used in the regional chemistry transport model COSMO–MUSCAT in a 2-D application. Besides sulfate and nitrate production, the mechanism treats a complex HOx-chemistry, transition metal ion chemistry and organic species up to C4. The effects of the cloud chemistry on the chemical composition of air and particles were investigated. Sensitivity studies were conducted for an urban and a rural air mass. For this purpose simulations with C3.0RED were compared to ones with a simple inorganic aqueous phase mechanism (INORG) and without aqueous phase chemistry. A reduction of the gas phase concentrations of major oxidants was observed especially in the urban environment. Compared to INORG, C3.0RED is always more acidic leading to shifts in several chemical subsystems, (e.g. production of sulfate). Using C3.0RED instead of INORG, differences in sulfate mass of 3% to −15% occurred. The modeled O/C-ratio tends to be higher than observations as C3.0RED does not consider the whole population of organics and no insoluble organic mass. Nevertheless, the modeled concentration of glyoxalic acid is in the range of atmospheric measurements in both environments, whereas oxalic acid and pyruvic acid are underestimated in the urban case.
- ItemA case of extreme particulate matter concentrations over Central Europe caused by dust emitted over the southern Ukraine(München : European Geopyhsical Union, 2008) Birmili, W.; Schepanski, K.; Ansmann, A.; Spindler, G.; Tegen, I.; Wehner, B.; Nowak, A.; Reimer, E.; Mattis, I.; Müller, K.; Brüggemann, E.; Gnauk, T.; Herrmann, H.; Wiedensohler, A.; Althausen, D.; Schladitz, A.; Tuch, T.; Löschau, G.On 24 March 2007, an extraordinary dust plume was observed in the Central European troposphere. Satellite observations revealed its origins in a dust storm in Southern Ukraine, where large amounts of soil were resuspended from dried-out farmlands at wind gusts up to 30 m s−1. Along the pathway of the plume, maximum particulate matter (PM10) mass concentrations between 200 and 1400 μg m−3 occurred in Slovakia, the Czech Republic, Poland, and Germany. Over Germany, the dust plume was characterised by a volume extinction coefficient up to 400 Mm−1 and a particle optical depth of 0.71 at wavelength 0.532 μm. In-situ size distribution measurements as well as the wavelength dependence of light extinction from lidar and Sun photometer measurements confirmed the presence of a coarse particle mode with diameters around 2–3 μm. Chemical particle analyses suggested a fraction of 75% crustal material in daily average PM10 and up to 85% in the coarser fraction PM10–2.5. Based on the particle characteristics as well as a lack of increased CO and CO2 levels, a significant impact of biomass burning was ruled out. The reasons for the high particle concentrations in the dust plume were twofold: First, dust was transported very rapidly into Central Europe in a boundary layer jet under dry conditions. Second, the dust plume was confined to a relatively stable boundary layer of 1.4–1.8 km height, and could therefore neither expand nor dilute efficiently. Our findings illustrate the capacity of combined in situ and remote sensing measurements to characterise large-scale dust plumes with a variety of aerosol parameters. Although such plumes from Southern Eurasia seem to occur rather infrequently in Central Europe, its unexpected features highlights the need to improve the description of dust emission, transport and transformation processes needs, particularly when facing the possible effects of further anthropogenic desertification and climate change.
- ItemReactive Halogens in the Marine Boundary Layer (RHaMBLe): The tropical North Atlantic experiments(München : European Geopyhsical Union, 2010) Lee, J.D.; McFiggans, G.; Allan, J.D.; Baker, A.R.; Ball, S.M.; Benton, A.K.; Carpenter, L.J.; Commane, R.; Finley, B.D.; Evans, M.; Fuentes, E.; Furneaux, K.; Goddard, A.; Good, N.; Hamilton, J.F.; Heard, D.E.; Herrmann, H.; Hollingsworth, A.; Hopkins, J.R.; Ingham, T.; Irwin, M.; Jones, C.E.; Jones, R.L.; Keene, W.C.; Lawler, M.J.; Lehmann, S.; Lewis, A.C.; Long, M.S.; Mahajan, A.; Methven, J.; Moller, S.J.; Müller, K.; Müller, T.; Niedermeier, N.; O'Doherty, S.; Oetjen, H.; Plane, J.M.C.; Pszenny, A.A.P.; Read, K.A.; Saiz-Lopez, A.; Saltzman, E.S.; Sander, R.; von Glasow, R.; Whalley, L.; Wiedensohler, A.; Young, D.The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.
- ItemTerpenylic acid and related compounds: precursors for dimers in secondary organic aerosol from the ozonolysis of α- and β-pinene(München : European Geopyhsical Union, 2010) Yasmeen, F.; Vermeylen, R.; Szmigielski, R.; Iinuma, Y.; Böge, O.; Herrmann, H.; Maenhaut, W.; Claeys, M.In the present study, we have characterized the structure of a higher-molecular weight (MW) 358 α- and β-pinene dimeric secondary organic aerosol (SOA) product that received ample attention in previous molecular characterization studies and has been elusive. Based on mass spectrometric evidence for deprotonated molecules formed by electrospray ionization in the negative ion mode and chemical considerations, it is suggested that diaterpenylic acid is a key monomeric intermediate for dimers of the ester type. It is proposed that cis-pinic acid is esterified with the hydroxyl-containing diaterpenylic acid, which can be explained through acid-catalyzed hydrolysis of the recently elucidated lactone-containing terpenylic acid and/or diaterpenylic acid acetate, both first-generation oxidation products. To a minor extent, higher-MW 358 and 344 diester products are formed containing other terpenoic acids as monomeric units, i.e., diaterpenylic acid instead of cis-pinic acid, and diaterebic acid instead of diaterpenylic acid. It is shown that the MW 358 diester and related MW 344 compounds, which can be regarded as processed SOA products, also occur in ambient fine (PM2.5) rural aerosol collected at night during the warm period of the 2006 summer field campaign conducted at K-puszta, Hungary, a rural site with coniferous vegetation. This indicates that, under ambient conditions, the higher-MW diesters are formed in the particle phase over a longer time-scale than that required for gas-to-particle partitioning of their monomeric precursors in laboratory α-/β-pinene ozonolysis experiments.
- ItemDiurnal variations of ambient particulate wood burning emissions and their contribution to the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) in Seiffen, Germany(München : European Geopyhsical Union, 2011) Poulain, L.; Iinuma, Y.; Müller, K.; Birmili, W.; Weinhold, K.; Brüggemann, E.; Gnauk, T.; Hausmann, A.; Löschau, G.; Wiedensohler, A.; Herrmann, H.Residential wood burning is becoming an increasingly important cause of air quality problems since it has become a popular source of alternative energy to fossil fuel. In order to characterize the contribution of residential wood burning to local particle pollution, a field campaign was organized at the village of Seiffen (Saxony, Germany). During this campaign, an Aerosol Mass Spectrometer (AMS) was deployed in parallel to a PM1 high volume filter sampler. The AMS mass spectra were analyzed using Positive Matrix Factorization (PMF) to obtain detailed information about the organic aerosol (OA). Biomass-burning organic aerosol (BBOA), Hydrocarbon-like organic aerosol (HOA), and Oxygenated Organic Aerosol (OOA) were identified and represented 20%, 17% and 62% of total OA, respectively. Additionally, Polycyclic Aromatic Hydrocarbons (PAH) were measured by the AMS with an average concentration of 10 ng m−3 and short term events of extremely high PAH concentration (up to 500 ng m−3) compared to the mean PAH value were observed during the whole measurement period. A comparison with the results from PM1 filter samples showed that the BBOA factor and the AMS PAH are good indicators of the total concentration of the different monosaccharide anhydrides and PAH measured on the filter samples. Based on its low correlation with CO and the low car traffic, the HOA factor was considered to be related to residential heating using liquid fuel. An influence of the time of the week (week vs. weekend) on the diurnal profiles of the different OA components was observed. The weekdays were characterized by two maxima; a first one early in the morning and a stronger one in the evening. During the weekend days, the different OA components principally reached only one maximum in the afternoon. Finally, the PAH emitted directly from residential wood combustion was estimated to represent 1.5% of the total mass of the BBOA factor and around 62% of the total PAH concentration measured at Seiffen. This result highlights the important contribution of residential wood combustion to air quality and PAH emissions at the sampling place, which might have a significant impact on human health. Moreover, it also emphasizes the need for a better time resolution of the chemical characterization of toxic particulate compounds in order to provide more information on variations of the different sources through the days as well as to better estimate the real human exposure.
- ItemChemical mass balance of 300 °c non-volatile particles at the tropospheric research site Melpitz, Germany(München : European Geopyhsical Union, 2014) Poulain, L.; Birmili, W.; Canonaco, F.; Crippa, M.; Wu, Z.J.; Nordmann, S.; Wiedensohler, A.; Held, A.; Spindler, G.; Prévôt, A.S.H.; Wiedensohler, A.; Herrmann, H.In the fine-particle mode (aerodynamic diameter < 1 μm) non-volatile material has been associated with black carbon (BC) and low-volatile organics and, to a lesser extent, with sea salt and mineral dust. This work analyzes non-volatile particles at the tropospheric research station Melpitz (Germany), combining experimental methods such as a mobility particle-size spectrometer (3–800 nm), a thermodenuder operating at 300 °C, a multi-angle absorption photometer (MAAP), and an aerosol mass spectrometer (AMS). The data were collected during two atmospheric field experiments in May–June 2008 as well as February–March 2009. As a basic result, we detected average non-volatile particle–volume fractions of 11 ± 3% (2008) and 17 ± 8% (2009). In both periods, BC was in close linear correlation with the non-volatile fraction, but not sufficient to quantitatively explain the non-volatile particle mass concentration. Based on the assumption that BC is not altered by the heating process, the non-volatile particle mass fraction could be explained by the sum of black carbon (47% in summer, 59% in winter) and a non-volatile organic contribution estimated as part of the low-volatility oxygenated organic aerosol (LV-OOA) (53% in summer, 41% in winter); the latter was identified from AMS data by factor analysis. Our results suggest that LV-OOA was more volatile in summer (May–June 2008) than in winter (February–March 2009) which was linked to a difference in oxidation levels (lower in summer). Although carbonaceous compounds dominated the sub-μm non-volatile particle mass fraction most of the time, a cross-sensitivity to partially volatile aerosol particles of maritime origin could be seen. These marine particles could be distinguished, however from the carbonaceous particles by a characteristic particle volume–size distribution. The paper discusses the uncertainty of the volatility measurements and outlines the possible merits of volatility analysis as part of continuous atmospheric aerosol measurements.
- ItemHydroxymethanesulfonic acid in size-segregated aerosol particles at nine sites in Germany(München : European Geopyhsical Union, 2014) Scheinhardt, S.; van Pinxteren, D.; Müller, K.; Spindler, G.; Herrmann, H.In the course of two field campaigns, size-segregated particle samples were collected at nine sites in Germany, including traffic, urban, rural, marine and mountain sites. During the chemical characterisation of the samples some of them were found to contain an unknown substance that was later identified as hydroxymethanesulfonic acid (HMSA). HMSA is known to be formed during the reaction of S(IV) (HSO3− or SO32−) with formaldehyde in the aqueous phase. Due to its stability, HMSA can act as a reservoir species for S(IV) in the atmosphere and is therefore of interest for the understanding of atmospheric sulfur chemistry. However, no HMSA data are available for atmospheric particles from central Europe, and even on a worldwide scale data are scarce. Thus, the present study now provides a representative data set with detailed information on HMSA concentrations in size-segregated central European aerosol particles. HMSA mass concentrations in this data set were highly variable: HMSA was found in 224 out of 738 samples (30%), sometimes in high mass concentrations exceeding those of oxalic acid. On average over all 154 impactor runs, 31.5 ng m−3 HMSA was found in PM10, contributing 0.21% to the total mass. The results show that the particle diameter, the sampling location, the sampling season and the air mass origin impact the HMSA mass concentration. Highest concentrations were found in the particle fraction 0.42–1.2 μm, at urban sites, in winter and with eastern (continental) air masses, respectively. The results suggest that HMSA is formed during aging of pollution plumes. A positive correlation of HMSA with sulfate, oxalate and PM is found (R2 > 0.4). The results furthermore suggest that the fraction of HMSA in PM slightly decreases with increasing pH.
- ItemIn-cloud sulfate addition to single particles resolved with sulfur isotope analysis during HCCT-2010(München : European Geopyhsical Union, 2014) Harris, E.; Sinha, B.; van Pinxteren, D.; Schneider, J.; Poulain, L.; Collett, J.; D'Anna, B.; Fahlbusch, B.; Foley, S.; Fomba, K.W.; George, C.; Gnauk, T.; Henning, S.; Lee, T.; Mertes, S.; Roth, A.; Stratmann, F.; Borrmann, S.; Hoppe, P.; Herrmann, H.In-cloud production of sulfate modifies aerosol size distribution, with important implications for the magnitude of indirect and direct aerosol cooling and the impact of SO2 emissions on the environment. We investigate which sulfate sources dominate the in-cloud addition of sulfate to different particle classes as an air parcel passes through an orographic cloud. Sulfate aerosol, SO2 and H2SO4 were collected upwind, in-cloud and downwind of an orographic cloud for three cloud measurement events during the Hill Cap Cloud Thuringia campaign in autumn 2010 (HCCT-2010). Combined SEM and NanoSIMS analysis of single particles allowed the δ34S of particulate sulfate to be resolved for particle size and type. The most important in-cloud SO2 oxidation pathway at HCCT-2010 was aqueous oxidation catalysed by transition metal ions (TMI catalysis), which was shown with single particle isotope analyses to occur primarily in cloud droplets nucleated on coarse mineral dust. In contrast, direct uptake of H2SO4 (g) and ultrafine particulate were the most important sources modifying fine mineral dust, increasing its hygroscopicity and facilitating activation. Sulfate addition to "mixed" particles (secondary organic and inorganic aerosol) and coated soot was dominated by in-cloud aqueous SO2 oxidation by H2O2 and direct uptake of H2SO4 (g) and ultrafine particle sulfate, depending on particle size mode and time of day. These results provide new insight into in-cloud sulfate production mechanisms, and show the importance of single particle measurements and models to accurately assess the environmental effects of cloud processing.