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- ItemThe chemistry of OH and HO2 radicals in the boundary layer over the tropical Atlantic Ocean(München : European Geopyhsical Union, 2010) Whalley, L.K.; Furneaux, K.L.; Goddard, A.; Lee, J.D.; Mahajan, A.; Oetjen, H.; Read, K.A.; Kaaden, N.; Carpenter, L.J.; Lewis, A.C.; Plane, J.M.C.; Saltzman, E.S.; Wiedensohler, A.; Heard, D.E.Fluorescence Assay by Gas Expansion (FAGE) has been used to detect ambient levels of OH and HO2 radicals at the Cape Verde Atmospheric Observatory, located in the tropical Atlantic marine boundary layer, during May and June 2007. Midday radical concentrations were high, with maximum concentrations of 9 ×106 molecule cm−3 and 6×108 molecule cm−3 observed for OH and HO2, respectively. A box model incorporating the detailed Master Chemical Mechanism, extended to include halogen chemistry, heterogeneous loss processes and constrained by all available measurements including halogen and nitrogen oxides, has been used to assess the chemical and physical parameters controlling the radical chemistry. The model was able to reproduce the daytime radical concentrations to within the 1 σ measurement uncertainty of 20% during the latter half of the measurement period but significantly under-predicted [HO2] by 39% during the first half of the project. Sensitivity analyses demonstrate that elevated [HCHO] (~2 ppbv) on specific days during the early part of the project, which were much greater than the mean [HCHO] (328 pptv) used to constrain the model, could account for a large portion of the discrepancy between modelled and measured [HO2] at this time. IO and BrO, although present only at a few pptv, constituted ~19% of the instantaneous sinks for HO2, whilst aerosol uptake and surface deposition to the ocean accounted for a further 23% of the HO2 loss at noon. Photolysis of HOI and HOBr accounted for ~13% of the instantaneous OH formation. Taking into account that halogen oxides increase the oxidation of NOx (NO → NO2), and in turn reduce the rate of formation of OH from the reaction of HO2 with NO, OH concentrations were estimated to be 9% higher overall due to the presence of halogens. The increase in modelled OH from halogen chemistry gives an estimated 9% shorter lifetime for methane in this region, and the inclusion of halogen chemistry is necessary to model the observed daily cycle of O3 destruction that is observed at the surface. Due to surface losses, we hypothesise that HO2 concentrations increase with height and therefore contribute a larger fraction of the O3 destruction than at the surface.
- ItemOn the formation of sulphuric acid – Amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation(München : European Geopyhsical Union, 2012) Paasonen, P.; Olenius, T.; Kupiainen, O.; Kurtén, T.; Petäjä, T.; Birmili, W.; Hamed, A.; Hu, M.; Huey, L.G.; Plass-Duelmer, C.; Smith, J.N.; Wiedensohler, A.; Loukonen, V.; McGrath, M.J.; Ortega, I.K.; Laaksonen, A.; Vehkamäki, H.; Kerminen, V.-M.; Kulmala, M.Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4).
- ItemChemistry of new particle growth in mixed urban and biogenic emissions - Insights from CARES(München : European Geopyhsical Union, 2014) Setyan, A.; Song, C.; Merkel, M.; Knighton, W.B.; Onasch, T.B.; Canagaratna, M.R.; Worsnop, D.R.; Wiedensohler, A.; Shilling, J.E.; Zhang, Q.Regional new particle formation and growth events (NPEs) were observed on most days over the Sacramento and western Sierra foothills area of California in June 2010 during the Carbonaceous Aerosols and Radiative Effect Study (CARES). Simultaneous particle measurements at both the T0 (Sacramento, urban site) and the T1 (Cool, rural site located ~40 km northeast of Sacramento) sites of CARES indicate that the NPEs usually occurred in the morning with the appearance of an ultrafine mode at ~15 nm (in mobility diameter, Dm, measured by a mobility particle size spectrometer operating in the range 10-858 nm) followed by the growth of this modal diameter to ~50 nm in the afternoon. These events were generally associated with southwesterly winds bringing urban plumes from Sacramento to the T1 site. The growth rate was on average higher at T0 (7.1 ± 2.7 nm h−1) than at T1 (6.2 ± 2.5 nm h−1), likely due to stronger anthropogenic influences at T0. Using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), we investigated the evolution of the size-resolved chemical composition of new particles at T1. Our results indicate that the growth of new particles was driven primarily by the condensation of oxygenated organic species and, to a lesser extent, ammonium sulfate. New particles appear to be fully neutralized during growth, consistent with high NH3 concentration in the region. Nitrogen-containing organic ions (i.e., CHN+, CH4N+, C2H3N+, and C2H4N+) that are indicative of the presence of alkyl-amine species in submicrometer particles enhanced significantly during the NPE days, suggesting that amines might have played a role in these events. Our results also indicate that the bulk composition of the ultrafine mode organics during NPEs was very similar to that of anthropogenically influenced secondary organic aerosol (SOA) observed in transported urban plumes. In addition, the concentrations of species representative of urban emissions (e.g., black carbon, CO, NOx, and toluene) were significantly higher whereas the photo-oxidation products of biogenic VOCs (volatile organic compounds) and the biogenically influenced SOA also increased moderately during the NPE days compared to the non-event days. These results indicate that the frequently occurring NPEs over the Sacramento and Sierra Nevada regions were mainly driven by urban plumes from Sacramento and the San Francisco Bay Area, and that the interaction of regional biogenic emissions with the urban plumes has enhanced the new particle growth. This finding has important implications for quantifying the climate impacts of NPEs on global scale.
- ItemEnhancement of atmospheric H2SO4/H2O nucleation: Organic oxidation products versus amines(München : European Geopyhsical Union, 2014) Berndt, T.; Sipilä, M.; Stratmann, F.; Petäjä, T.; Vanhanen, J.; Mikkilä, J.; Patokoski, J.; Taipale, R.; Mauldin III, R.L.; Kulmala, M.Atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research – Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 107–108 molecule cm−3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm−3. Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~107 molecule cm−3. Furthermore, the findings confirm the appearance of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 107–1010 molecule cm−3 applying photolytic OH radical generation for H2SO4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine < aniline < dimethylamine < trimethylamine. This result supports the idea of H2SO4 cluster stabilization by amines due to strong H2SO4↔amine interactions. On the other hand, this study indicates that for organic oxidation products (in presence of the possible amine background as stated) a distinct H2SO4 / H2O nucleation enhancement can be due to increased H2SO4 formation caused by additional organic oxidant production (sCI) rather than by stabilization of H2SO4 clusters due to H2SO4↔organics interactions.
- ItemCharacterisation and optimisation of a sample preparation method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium(München : European Geopyhsical Union, 2015) Rodigast, M.; Mutzel, A.; Iinuma, Y.; Haferkorn, S.; Herrmann, H.Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds. Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). With the present method quantification can be carried out for each carbonyl compound originating from fog, cloud and rain or sampled from the gas- and particle phase in water. Detection limits between 0.01 and 0.17 μmol L−1 were found, depending on carbonyl compounds. Furthermore, best results were found for the derivatisation with a PFBHA concentration of 0.43 mg mL−1 for 24 h followed by a subsequent extraction with dichloromethane for 30 min at pH = 1. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione after a reaction time of 5 h.
- ItemDevelopment of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds(Katlenburg-Lindau : EGU, 2019) Bräuer, Peter; Mouchel-Vallon, Camille; Tilgner, Andreas; Mutzel, Anke; Böge, Olaf; Rodigast, Maria; Poulain, Laurent; van Pinxteren, Dominik; Wolke, Ralf; Aumont, Bernard; Herrmann, HartmutThis paper presents a new CAPRAM-GECKOA protocol for mechanism auto-generation of aqueous-phase organic processes. For the development, kinetic data in the literature were reviewed and a database with 464 aqueousphase reactions of the hydroxyl radical with organic compounds and 130 nitrate radical reactions with organic compounds has been compiled and evaluated. Five different methods to predict aqueous-phase rate constants have been evaluated with the help of the kinetics database: gas-aqueous phase correlations, homologous series of various compound classes, radical reactivity comparisons, Evans-Polanyi-type correlations, and structure-activity relationships (SARs). The quality of these prediction methods was tested as well as their suitability for automated mechanism construction. Based on this evaluation, SARs form the basis of the new CAPRAM-GECKO-A protocol. Evans-Polanyi-type correlations have been advanced to consider all available H atoms in a molecule besides the H atoms with only the weakest bond dissociation enthalpies (BDEs). The improved Evans- Polanyi-type correlations are used to predict rate constants for aqueous-phase NO3 and organic compounds reactions. Extensive tests have been performed on essential parameters and on highly uncertain parameters with limited experimental data. These sensitivity studies led to further improvements in the new CAPRAM-GECKO-A protocol but also showed current limitations. Biggest uncertainties were observed in uptake processes and the estimation of Henry's law coefficients as well as radical chemistry, in particular the degradation of alkoxy radicals. Previous estimation methods showed several deficits, which impacted particle growth. For further evaluation, a 1,3,5-trimethylbenzene oxidation experiment has been performed in the aerosol chamber "Leipziger Aerosolkammer" (LEAK) at high relative humidity conditions and compared to a multiphase mechanism using the Master Chemical Mechanism (MCMv3.2) in the gas phase and using a methylglyoxal oxidation scheme of about 600 reactions generated with the new CAPRAM-GECKO-A protocol in the aqueous phase. While it was difficult to evaluate single particle constituents due to concentrations close to the detection limits of the instruments applied, the model studies showed the importance of aqueous-phase chemistry in respect to secondary organic aerosol (SOA) formation and particle growth. The new protocol forms the basis for further CAPRAM mechanism development towards a new version 4.0. Moreover, it can be used as a supplementary tool for aerosol chambers to design and analyse experiments of chemical complexity and help to understand them on a molecular level. © 2019 Author(s).
- ItemRelating particle hygroscopicity and CCN activity to chemical composition during the HCCT-2010 field campaign(München : European Geopyhsical Union, 2013) Wu, Z.J.; Poulain, L.; Henning, S.; Dieckmann, K.; Birmili, W.; Merkel, M.; van Pinxteren, D.; Spindler, G.; Müller, K.; Stratmann, F.; Herrmann, H.; Wiedensohler, A.Particle hygroscopic growth at 90% RH (relative humidity), cloud condensation nuclei (CCN) activity, and size-resolved chemical composition were concurrently measured in the Thüringer Wald mid-level mountain range in central Germany in the fall of 2010. The median hygroscopicity parameter values, κ, of 50, 75, 100, 150, 200, and 250 nm particles derived from hygroscopicity measurements are respectively 0.14, 0.14, 0.17, 0.21, 0.24, and 0.28 during the sampling period. The closure between HTDMA (Hygroscopicity Tandem Differential Mobility Analyzers)-measured (κHTDMA) and chemical composition-derived (κchem) hygroscopicity parameters was performed based on the Zdanovskii–Stokes–Robinson (ZSR) mixing rule. Using size-averaged chemical composition, the κ values are substantially overpredicted (30 and 40% for 150 and 100 nm particles). Introducing size-resolved chemical composition substantially improved closure. We found that the evaporation of NH4NO3, which may happen in a HTDMA system, could lead to a discrepancy in predicted and measured particle hygroscopic growth. The hygroscopic parameter of the organic fraction, κorg, is positively correlated with the O : C ratio (κorg = 0.19 × (O : C) − 0.03). Such correlation is helpful to define the κorg value in the closure study. κ derived from CCN measurement was around 30% (varied with particle diameters) higher than that determined from particle hygroscopic growth measurements (here, hydrophilic mode is considered only). This difference might be explained by the surface tension effects, solution non-ideality, gas-particle partitioning of semivolatile compounds, and the partial solubility of constituents or non-dissolved particle matter. Therefore, extrapolating from HTDMA data to properties at the point of activation should be done with great care. Finally, closure study between CCNc (cloud condensation nucleus counter)-measured (κCCN) and chemical composition (κCCN, chem) was performed using CCNc-derived κ values for individual components. The results show that the κCCN can be well predicted using particle size-resolved chemical composition and the ZSR mixing rule.
- ItemThe simulations of sulfuric acid concentration and new particle formation in an urban atmosphere in China(München : European Geopyhsical Union, 2013) Wang, Z.B.; Hu, M.; Mogensen, D.; Yue, D.L.; Zheng, J.; Zhang, R.Y.; Liu, Y.; Yuan, B.; Li, X.; Shao, M.; Zhou, L.; Wu, Z.J.; Wiedensohler, A.; Boy, M.Simulations of sulfuric acid concentration and new particle formation are performed by using the zero-dimensional version of the model MALTE (Model to predict new Aerosol formation in the Lower TropospherE) and measurements from the Campaign of Air Quality Research in Beijing and Surrounding areas (CAREBeijing) in 2008. Chemical reactions from the Master Chemical Mechanism version 3.2 (MCM v3.2) are used in the model. High correlation (slope = 0.72, R = 0.74) between the modelled and observed sulfuric acid concentrations is found during daytime (06:00–18:00). The aerosol dynamics are simulated by the University of Helsinki Multicomponent Aerosol (UHMA) model including several nucleation mechanisms. The results indicate that the model is able to predict the on- and offset of new particle formation in an urban atmosphere in China. In addition, the number concentrations of newly formed particles in kinetic-type nucleation including homogenous homomolecular (J=K[H2SO4]2) and homogenous heteromolecular nucleation involving organic vapours (J=Khet[H2SO4][Org]) are in satisfactory agreement with the observations. However, the specific organic compounds that possibly participate in the nucleation process should be investigated in further studies. For the particle growth, only a small fraction of the oxidized total organics condense onto the particles in polluted environments. Meanwhile, the OH and O3 oxidation mechanism contribute 5.5% and 94.5% to the volume concentration of small particles, indicating the particle growth is more controlled by the precursor gases and their oxidation by O3.
- ItemExperimental investigation of ion-ion recombination under atmospheric conditions(München : European Geopyhsical Union, 2015) Franchin, A.; Ehrhart, S.; Leppä, J.; Nieminen, T.; Gagné, S.; Schobesberger, S.; Wimmer, D.; Duplissy, J.; Riccobono, F.; Dunne, E.M.; Rondo, L.; Downard, A.; Bianchi, F.; Kupc, A.; Tsagkogeorgas, G.; Lehtipalo, K.; Manninen, H.E.; Almeida, J.; Amorim, A.; Wagner, P.E.; Hansel, A.; Kirkby, J.; Le Rille, O.; Kürten, A.; Donahue, N.M.; Makhmutov, V.; Mathot, S.; Metzger, A.; Petäjä, T.; Schnitzhofer, R.; Sipilä, M.; Stozhkov, Y.; Tomé, A.; Kerminen, V.-M.; Carslaw, K.; Curtius, J.; Baltensperger, U.; Kulmala, M.We present the results of laboratory measurements of the ion–ion recombination coefficient at different temperatures, relative humidities and concentrations of ozone and sulfur dioxide. The experiments were carried out using the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at CERN, the walls of which are made of conductive material, making it possible to measure small ions. We produced ions in the chamber using a 3.5 GeV c−1 beam of positively charged pions (π+) generated by the CERN Proton Synchrotron (PS). When the PS was switched off, galactic cosmic rays were the only ionization source in the chamber. The range of the ion production rate varied from 2 to 100 cm−3 s−1, covering the typical range of ionization throughout the troposphere. The temperature ranged from −55 to 20 °C, the relative humidity (RH) from 0 to 70 %, the SO2 concentration from 0 to 40 ppb, and the ozone concentration from 200 to 700 ppb. The best agreement of the retrieved ion–ion recombination coefficient with the commonly used literature value of 1.6 × 10−6 cm3 s−1 was found at a temperature of 5 °C and a RH of 40 % (1.5 ± 0.6) × 10−6 cm3 s−1. At 20 °C and 40 % RH, the retrieved ion–ion recombination coefficient was instead (2.3 ± 0.7) × 10−6 cm3 s−1. We observed no dependency of the ion–ion recombination coefficient on ozone concentration and a weak variation with sulfur dioxide concentration. However, we observed a more than fourfold increase in the ion–ion recombination coefficient with decreasing temperature. We compared our results with three different models and found an overall agreement for temperatures above 0 °C, but a disagreement at lower temperatures. We observed a strong increase in the recombination coefficient for decreasing relative humidities, which has not been reported previously.
- ItemHydroxyl layer: trend of number density and intra-annual variability(Katlenburg, Lindau : Copernicus, 2015) Sonnemann, G.R.; Hartogh, P.; Berger, U.; Grygalashvyly, M.The layer of vibrationally excited hydroxyl (OH*) near the mesopause in Earth's atmosphere is widely used to derive the temperature at this height and to observe dynamical processes such as gravity waves. The concentration of OH* is controlled by the product of atomic hydrogen, with ozone creating a layer of enhanced concentration in the mesopause region. However, the basic influences on the OH* layer are atomic oxygen and temperature. The long-term monitoring of this layer provides information on a changing atmosphere. It is important to know which proportion of a trend results from anthropogenic impacts on the atmosphere and which proportion reflects natural variations. In a previous paper (Grygalashvyly et al., 2014), the trend of the height of the layer and the trend in temperature were investigated particularly in midlatitudes on the basis of our coupled dynamic and chemical transport model LIMA (Leibniz Institute Middle Atmosphere). In this paper we consider the trend for the number density between the years 1961 and 2009 and analyze the reason of the trends on a global scale. Further, we consider intra-annual variations. Temperature and wind have the strongest impacts on the trend. Surprisingly, the increase in greenhouse gases (GHGs) has no clear influence on the chemistry of OH*. The main reason for this lies in the fact that, in the production term of OH*, if atomic hydrogen increases due to increasing humidity of the middle atmosphere by methane oxidation, ozone decreases. The maximum of the OH* layer is found in the mesopause region and is very variable. The mesopause region is a very intricate domain marked by changeable dynamics and strong gradients of all chemically active minor constituents determining the OH* chemistry. The OH* concentration responds, in part, very sensitively to small changes in these parameters. The cause for this behavior is given by nonlinear reactions of the photochemical system being a nonlinear enforced chemical oscillator driven by the diurnal-periodic solar insolation. At the height of the OH* layer the system operates in the vicinity of chemical resonance. The solar cycle is mirrored in the data, but the long-term behavior due to the trend in the Lyman-α radiation is very small. The number density shows distinct hemispheric differences. The calculated OH* values show sometimes a step around a certain year. We introduce a method to find out the date of this step and discuss a possible reason for such behavior.