2017, Brüggemann, Martin, Poulain, Laurent, Held, Andreas, Stelzer, Torsten, Zuth, Christoph, Richters, Stefanie, Mutzel, Anke, van Pinxteren, Dominik, Iinuma, Yoshiteru, Katkevica, Sarmite, Rabe, René, Herrmann, Hartmut, Hoffmann, Thorsten

The chemical composition of ambient organic aerosols was analyzed using complementary mass spectrometric techniques during a field study in central Europe in July 2014 (Fichtelgebirge – Biogenic Emission and Aerosol Chemistry, F-BEACh 2014). Among several common biogenic secondary organic aerosol (BSOA) marker compounds, 93 acidic oxygenated hydrocarbons were detected with elevated abundances and were thus attributed to be characteristic for the organic aerosol mass at the site. Monoterpene measurements exhibited median mixing ratios of 1.6 and 0.8 ppbV for in and above canopy levels respectively. Nonetheless, concentrations for early-generation oxidation products were rather low, e.g., pinic acid (c  =  4.7 (±2.5) ng m−3). In contrast, high concentrations were found for later-generation photooxidation products such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA, c  =  13.8 (±9.0) ng m−3) and 3-carboxyheptanedioic acid (c  =  10.2 (±6.6) ng m−3), suggesting that aged aerosol masses were present during the campaign period. In agreement, HYSPLIT trajectory calculations indicate that most of the arriving air masses traveled long distances (>  1500 km) over land with high solar radiation. In addition, around 47 % of the detected compounds from filter sample analysis contained sulfur, confirming a rather high anthropogenic impact on biogenic emissions and their oxidation processes. Among the sulfur-containing compounds, several organosulfates, nitrooxy organosulfates, and highly oxidized organosulfates (HOOS) were tentatively identified by high-resolution mass spectrometry. Correlations among HOOS, sulfate, and highly oxidized multifunctional organic compounds (HOMs) support the hypothesis of previous studies that HOOS are formed by reactions of gas-phase HOMs with particulate sulfate. Moreover, periods with high relative humidity indicate that aqueous-phase chemistry might play a major role in HOOS production. However, for dryer periods, coinciding signals for HOOS and gas-phase peroxyradicals (RO2•) were observed, suggesting RO2• to be involved in HOOS formation.

2017, Coluzza, Ivan, Creamean, Jessie, Rossi, Michel J., Wex, Heike, Alpert, Peter Aaron, Bianco, Valentino, Boose, Yvonne, Dellago, Christoph, Felgitsch, Laura, Fröhlich-Nowoisky, Janine, Herrmann, Hartmut, Jungblut, Swetlana, Kanji, Zamin A., Menzl, Georg, Moffett, Bruce, Moritz, Clemens, Mutzel, Anke, Pöschl, Ulrich, Schauperl, Michael, Scheel, Jan, Stopelli, Emiliano, Stratmann, Frank, Grothe, Hinrich, Schmale, David G.

There has been increasing interest in ice nucleation research in the last decade. To identify important gaps in our knowledge of ice nucleation processes and their impacts, two international workshops on ice nucleation were held in Vienna, Austria in 2015 and 2016. Experts from these workshops identified the following research needs: (1) uncovering the molecular identity of active sites for ice nucleation; (2) the importance of modeling for the understanding of heterogeneous ice nucleation; (3) identifying and quantifying contributions of biological ice nuclei from natural and managed environments; (4) examining the role of aging in ice nuclei; (5) conducting targeted sampling campaigns in clouds; and (6) designing lab and field experiments to increase our understanding of the role of ice-nucleating particles in the atmosphere. Interdisciplinary teams of scientists should work together to establish and maintain a common, unified language for ice nucleation research. A number of commercial applications benefit from ice nucleation research, including the production of artificial snow, the freezing and preservation of water-containing food products, and the potential modulation of weather. Additional work is needed to increase our understanding of ice nucleation processes and potential impacts on precipitation, water availability, climate change, crop health, and feedback cycles.

2017, Kecorius, Simonas, Ma, Nan, Teich, Monique, van Pinxteren, Dominik, Zhang, Shenglan, Gröβ, Johannes, Spindler, Gerald, Müller, Konrad, Iinuma, Yoshiteru, Hu, Min, Herrmann, Hartmut, Wiedensohler, Alfred

Particulate emissions from crop residue burning decrease the air quality as well as influence aerosol radiative properties on a regional scale. The North China Plain (NCP) is known for the large scale biomass burning (BB) of field residues, which often results in heavy haze pollution episodes across the region. We have been able to capture a unique BB episode during the international CAREBeijing-NCP intensive field campaign in Wangdu in the NCP (38.6°N, 115.2°E) from June to July 2014. It was found that aerosol particles originating from this BB event showed a significantly different mixing state compared with clean and non-BB pollution episodes. BB originated particles showed a narrower probability density function (PDF) of shrink factor (SF). And the maximum was found at shrink factor of 0.6, which is higher than in other episodes. The non-volatile particle number fraction during the BB episode decreased to 3% and was the lowest measured value compared to all other predefined episodes. To evaluate the influence of particle mixing state on aerosol single scattering albedo (SSA), SSA at different RHs was simulated using the measured aerosol physical-chemical properties. The differences between the calculated SSA for biomass burning, clean and pollution episodes are significant, meaning that the variation of SSA in different pollution conditions needs to be considered in the evaluation of aerosol direct radiative effects in the NCP. And the calculated SSA was found to be quite sensitive on the mixing state of BC, especially at low-RH condition. The simulated SSA was also compared with the measured values. For all the three predefined episodes, the measured SSA are very close to the calculated ones with assumed mixing states of homogeneously internal and core-shell internal mixing, indicating that both of the conception models are appropriate for the calculation of ambient SSA in the NCP.

2017, Ng, Nga Lee, Brown, Steven S., Archibald, Alexander T., Atlas, Elliot, Cohen, Ronald C., Crowley, John N., Day, Douglas A., Donahue, Neil M., Fry, Juliane L., Fuchs, Hendrik, Griffin, Robert J., Guzman, Marcelo I., Herrmann, Hartmut, Hodzic, Alma, Iinuma, Yoshiteru, Jimenez, José L., Kiendler-Scharr, Astrid, Lee, Ben H., Luecken, Deborah J., Mao, Jingqiu, McLaren, Robert, Mutzel, Anke, Osthoff, Hans D., Ouyang, Bin, Picquet-Varrault, Benedicte, Platt, Ulrich, Pye, Havala O.T., Rudich, Yinon, Schwantes, Rebecca H., Shiraiwa, Manabu, Stutz, Jochen, Thornton, Joel A., Tilgner, Andreas, Williams, Brent J., Zaveri, Rahul A.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

2017, Li, Jiarong, Wang, Xinfeng, Chen, Jianmin, Zhu, Chao, Li, Weijun, Li, Chengbao, Liu, Lu, Xu, Caihong, Wen, Liang, Xue, Likun, Wang, Wenxing, Ding, Aijun, Herrmann, Hartmut

The chemical composition of 39 cloud samples and droplet size distributions in 24 cloud events were investigated at the summit of Mt. Tai from July to October 2014. Inorganic ions, organic acids, metals, HCHO, H2O2, sulfur( IV), organic carbon, and elemental carbon as well as pH and electrical conductivity were analyzed. The acidity of the cloud water significantly decreased from a reported value of pH 3.86 during 2007-2008 (Guo et al., 2012) to pH 5.87 in the present study. The concentrations of nitrate and ammonium were both increased since 2007-2008, but the overcompensation of ammonium led to an increase in the mean pH value. The microphysical properties showed that cloud droplets were smaller than 26.0 μm and most were in the range of 6.0-9.0 μm at Mt. Tai. The maximum droplet number concentration (Nd) was associated with a droplet size of 7.0 μm. High liquid water content (LWC) values could facilitate the formation of larger cloud droplets and broadened the droplet size distribution. Cloud droplets exhibited a strong interaction with atmospheric aerosols. Higher PM2.5 levels resulted in higher concentrations of water-soluble ions and smaller sizes with increased numbers of cloud droplets. The lower pH values were likely to occur at higher PM2.5 concentrations. Clouds were an important sink for soluble materials in the atmosphere. The dilution effect of cloud water should be considered when estimating concentrations of soluble components in the cloud phase.

2017, Rodigast, Maria, Mutzel, Anke, Herrmann, Hartmut

Methylglyoxal forms oligomeric compounds in the atmospheric aqueous particle phase, which could establish a significant contribution to the formation of aqueous secondary organic aerosol (aqSOA). Thus far, no suitable method for the quantification of methylglyoxal oligomers is available despite the great effort spent for structure elucidation. In the present study a simplified method was developed to quantify heat-decomposable methylglyoxal oligomers as a sum parameter. The method is based on the thermal decomposition of oligomers into methylglyoxal monomers. Formed methylglyoxal monomers were detected using PFBHA (O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride) derivatisation and gas chromatography-mass spectrometry (GC/MS) analysis. The method development was focused on the heating time (varied between 15 and 48h), pH during the heating process (pH Combining double low line 1-7), and heating temperature (50, 100°C). The optimised values of these method parameters are presented. The developed method was applied to quantify heat-decomposable methylglyoxal oligomers formed during the OH-radical oxidation of 1,3,5-trimethylbenzene (TMB) in the Leipzig aerosol chamber (LEipziger AerosolKammer, LEAK). Oligomer formation was investigated as a function of seed particle acidity and relative humidity. A fraction of heat-decomposable methylglyoxal oligomers of up to 8% in the produced organic particle mass was found, highlighting the importance of those oligomers formed solely by methylglyoxal for SOA formation. Overall, the present study provides a new and suitable method for quantification of heat-decomposable methylglyoxal oligomers in the aqueous particle phase.

2017, Teich, Monique, van Pinxteren, Dominik, Wang, Michael, Kecorius, Simonas, Wang, Zhibin, Müller, Thomas, Močnik, Griša, Herrmann, Hartmut

The relative contributions of eight nitrated aromatic compounds (NACs: nitrophenols and nitrated salicylic acids) to the light absorption of aqueous particle extracts and particulate brown carbon were determined from aerosol particle samples collected in Germany and China. High-volume filter samples were collected during six campaigns, performed at five locations in two seasons: (I) two campaigns with strong influence of biomass-burning (BB) aerosol at the TROPOS institute (winter, 2014, urban background, Leipzig, Germany) and the Melpitz research site (winter, 2014, rural background); (II) two campaigns with strong influence from biogenic emissions at Melpitz (summer, 2014) and the forest site Waldstein (summer, 2014, Fichtelgebirge, Germany); and (III) two CAREBeijing-NCP campaigns at Xianghe (summer, 2013, anthropogenic polluted background) and Wangdu (summer, 2014, anthropogenic polluted background with a distinct BB episode), both in the North China Plain. The filter samples were analyzed for NAC concentrations and the light absorption of aqueous filter extracts was determined. Light absorption properties of particulate brown carbon were derived from a seven-wavelength aethalometer during the campaigns at TROPOS (winter) and Waldstein (summer). The light absorption of the aqueous filter extracts was found to be pH dependent, with larger values at higher pH. In general, the aqueous light absorption coefficient (Abs370) ranged from 0.21 to 21.8 Mm−1 under acidic conditions and 0.63 to 27.2 Mm−1 under alkaline conditions, over all campaigns. The observed mass absorption efficiency (MAE370) was in a range of 0.10–1.79 m2 g−1 and 0.24–2.57 m2 g−1 for acidic and alkaline conditions, respectively. For MAE370 and Abs370, the observed values were higher in winter than in summer, in agreement with other studies. The lowest MAE was observed for the Waldstein (summer) campaign (average of 0.17 ± 0.03 m2 g−1), indicating that freshly emitted biogenic aerosols are only weakly absorbing. In contrast, a strong relationship was found between the light absorption properties and the concentrations of levoglucosan, corroborating findings from other studies. Regarding the particulate light absorption at 370 nm, a mean particulate light absorption coefficient babs, 370 of 54 Mm−1 and 6.0 Mm−1 was determined for the TROPOS (winter) and Waldstein (summer) campaigns, respectively, with average contributions of particulate brown carbon to babs, 370 of 46 % at TROPOS (winter) and 15 % at Waldstein (summer). Thus, the aethalometer measurements support the findings from aqueous filter extracts of only weakly absorbing biogenic aerosols in comparison to the more polluted and BB influenced aerosol at TROPOS (winter). The mean contribution of NACs to the aqueous extract light absorption over all campaigns ranged from 0.10 to 1.25 % under acidic conditions and 0.13 to 3.71 % under alkaline conditions. The high variability among the measurement sites showed that the emission strengths of light-absorbing compounds and the composition of brown carbon were very different for each site. The mean contribution of NACs to the particulate brown carbon light absorption was 0.10 ± 0.06 % (acidic conditions) and 0.13 ± 0.09 % (alkaline conditions) during the Waldstein (summer) campaign and 0.25 ± 0.21 % (acidic conditions) and 1.13 ± 1.03 % (alkaline conditions) during the TROPOS (winter) campaign.

2017, Mu, Qing, Lammel, Gerhard, Gencarelli, Christian N., Hedgecock, Ian M., Chen, Ying, Přibylová, Petra, Teich, Monique, Zhang, Yuxuan, Zheng, Guangjie, van Pinxteren, Dominik, Zhang, Qiang, Herrmann, Hartmut, Shiraiwa, Manabu, Spichtinger, Peter, Su, Hang, Pöschl, Ulrich, Cheng, Yafang

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRF-Chem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

2017, Engel, Anja, Bange, Hermann W., Cunliffe, Michael, Burrows, Susannah M., Friedrichs, Gernot, Galgani, Luisa, Herrmann, Hartmut, Hertkorn, Norbert, Johnson, Martin, Liss, Peter S., Quinn, Patricia K., Schartau, Markus, Soloviev, Alexander, Stolle, Christian, Upstill-Goddard, Robert C., van Pinxteren, Manuela, Zäncker, Birthe

Despite the huge extent of the ocean's surface, until now relatively little attention has been paid to the sea surface microlayer (SML) as the ultimate interface where heat, momentum and mass exchange between the ocean and the atmosphere takes place. Via the SML, large-scale environmental changes in the ocean such as warming, acidification, deoxygenation, and eutrophication potentially influence cloud formation, precipitation, and the global radiation balance. Due to the deep connectivity between biological, chemical, and physical processes, studies of the SML may reveal multiple sensitivities to global and regional changes. Understanding the processes at the ocean's surface, in particular involving the SML as an important and determinant interface, could therefore provide an essential contribution to the reduction of uncertainties regarding ocean-climate feedbacks. This review identifies gaps in our current knowledge of the SML and highlights a need to develop a holistic and mechanistic understanding of the diverse biological, chemical, and physical processes occurring at the ocean-atmosphere interface. We advocate the development of strong interdisciplinary expertise and collaboration in order to bridge between ocean and atmospheric sciences. Although this will pose significant methodological challenges, such an initiative would represent a new role model for interdisciplinary research in Earth System sciences.

2017, Schneider, Johannes, Mertes, Stephan, van Pinxteren, Dominik, Herrmann, Hartmut, Borrmann, Stephan

Concurrent in situ analyses of interstitial aerosol and cloud droplet residues have been conducted at the Schmücke mountain site during the Hill Cap Cloud Thuringia campaign in central Germany in September and October 2010. Cloud droplets were sampled from warm clouds (temperatures between −3 and +16 °C) by a counterflow virtual impactor and the submicron-sized residues were analyzed by a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), while the interstitial aerosol composition was measured by an high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). During cloud-free periods, the submicron out-of-cloud aerosol was analyzed using both instruments, allowing for intercomparison between the two instruments. Further instrumentation included black carbon measurements and optical particle counters for the aerosol particles as well as optical sizing instrumentation for the cloud droplets. The results show that, under cloud conditions, on average 85 % of the submicron aerosol mass partitioned into the cloud liquid phase. Scavenging efficiencies of nitrate, ammonium, sulfate, and organics ranged between 60 and 100 %, with nitrate having, in general, the highest values. For black carbon, the scavenging efficiency was markedly lower (about 24 %). The nitrate and ammonium mass fractions were found to be markedly enhanced in cloud residues, indicating uptake of gaseous nitric acid and ammonia into the aqueous phase. This effect was found to be temperature dependent: at lower temperatures, the nitrate and ammonium mass fractions in the residues were higher. Also, the oxidation state of the organic matter in cloud residues was found to be temperature dependent: the O : C ratio was lower at higher temperatures. A possible explanation for this observation is a more effective uptake and/or higher concentrations of low-oxidized water-soluble volatile organic compounds, possibly of biogenic origin, at higher temperatures. Organic nitrates were observed in cloud residuals as well as in the out-of-cloud aerosol, but no indication of a preferred partitioning of organic nitrates into the aqueous phase or into the gas phase was detected. Assuming the uptake of nitric acid and ammonia in cloud droplets will be reversible, it will lead to a redistribution of nitrate and ammonium among the aerosol particles, leading to more uniform, internally mixed particles after several cloud passages.