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- ItemPhotocurrent modelling and experimental confirmation for meteoric smoke particle detectors on board atmospheric sounding rockets(Katlenburg-Lindau : Copernicus, 2018-9-20) Giono, Gabriel; Strelnikov, Boris; Asmus, Heiner; Staszak, Tristan; Ivchenko, Nickolay; Lübken, Franz-JosefCharacterising the photoelectron current induced by the Sun's UV radiation is crucial to ensure accurate daylight measurements from particle detectors. This article lays out the methodology used to address this problem in the case of the meteoric smoke particle detectors (MSPDs), developed by the Leibniz Institute of Atmospheric Physics in Kühlungsborn (IAP) and flown on board the PMWEs (Polar Mesosphere Winter Echoes) sounding rockets in April 2018. The methodology focuses on two complementary aspects: modelling and experimental measurements. A detailed model of the MSPD photocurrent was created based on the expected solar UV flux, the atmospheric UV absorption as a function of height by molecular oxygen and ozone, the photoelectric yield of the material coating the MSPD as a function of wavelength, the index of refraction of these materials as a function of wavelength and the angle of incidence of the illumination onto the MSPD. Due to its complex structure, composed of a central electrode shielded by two concentric grids, extensive ray-tracing calculations were conducted to obtain the incidence angles of the illumination on the central electrode, and this was done for various orientations of the MSPD in respect to the Sun. Results of the modelled photocurrent at different heights and for different materials, as well as for different orientations of the detector, are presented. As a pre-flight confirmation, the model was used to reproduce the experimental measurements conducted by Robertson et al. (2014) and agrees within an order of magnitude. An experimental setup for the calibration of the MSPD photocurrent is also presented. The photocurrent induced by the Lyman-alpha line from a deuterium lamp was recorded inside a vacuum chamber using a narrowband filter, while a UV-sensitive photodiode was used to monitor the UV flux. These measurements were compared with the model prediction, and also matched within an order of magnitude. Although precisely modelling the photocurrent is a challenging task, this article quantitatively improved the understanding of the photocurrent on the MSPD and discusses possible strategies to untangle the meteoric smoke particles (MSPs) current from the photocurrent recorded in-flight.
- ItemLong-term behavior of the concentration of the minor constituents in the mesosphere-a model study(Göttingen : Copernicus, 2009) Grygalashvyly, M.; Sonnemann, G.R.; Hartogh, P.We investigate the influence the rising concentrations of methane, nitrous oxide and carbon dioxide which have occurred since the pre-industrial era, have had on the chemistry of the mesosphere. For this investigation we use our global 3-D-model COMMA-IAP which was designed for the exploration of the MLT-region and in particular the extended mesopause region. Assumptions and approximations for the trends in the Lyman-flux (needed for the water vapor dissociation rate), methane and the water vapor mixing ratio at the hygropause are necessary to accomplish this study. To approximate the solar Lyman-α flux back to the pre-industrial time, we derived a quadratic fit using the sunspot number record which extends back to 1749 and is the only solar proxy available for the Lyman-α flux prior to 1947. We assume that methane increases with a constant growth rate from the pre-industrial era to the present. An unsolved problem for the model calculations consists of how the water vapor mixing ratio at the hygropause should be specified during this period. We assume that the hygropause was dryer during pre-industrial times than the present. As a consequence of methane oxidation, the model simulation indicates that the middle atmosphere has become more humid as a result of the rising methane concentration, but with some dependence on height and with a small time delay of few years. The solar influence on the water vapor mixing ratio is insignificant below about 80 km in summer high latitudes, but becomes increasingly more important above this altitude. The enhanced water vapor concentration increasesthe hydrogen radical concentration and reduces the mesospheric ozone. A second region of stronger ozone decrease is located in the vicinity of the stratopause. Increases in CO2 concentration enhance slightly the concentration of CO in the mesosphere. However, its influence upon the chemistry is small and its main effect is connected with a cooling of the upper atmosphere. The long-term behavior of water vapor is discussed in particular with respect to its impact on the NLC region.
- ItemParticle hygroscopicity during atmospheric new particle formation events: Implications for the chemical species contributing to particle growth(Göttingen : Copernicus, 2013) Wu, Z.; Birmili, W.; Poulain, L.; Poulain, L.; Merkel, M.; Fahlbusch, B.; Van Pinxteren, D.; Herrmann, H.; Wiedensohler, A.This study examines the hygroscopicity of newly formed particles (diameters range 25-45 nm) during two atmospheric new particle formation (NPF) events in the German mid-level mountains during the Hill Cap Cloud Thuringia 2010 (HCCT-2010) field experiment. At the end of the NPF event involving clear particle growth, we measured an unusually high soluble particle fraction of 58.5% at 45 nm particle size. The particle growth rate contributed through sulfuric acid condensation only accounts for around 6.5% of the observed growth rate. Estimations showed that sulfuric acid condensation explained, however, only around 10% of that soluble particle fraction. Therefore, the formation of additional water-soluble matter appears imperative to explain the missing soluble fraction. Although direct evidence is missing, we consider water-soluble organics as candidates for this mechanism. For the case with clear growth process, the particle growth rate was determined by two alternative methods based on tracking the mode diameter of the nucleation mode. The mean particle growth rate obtained from the inter-site data comparison using Lagrangian consideration is 3.8 (± 2.6) nm h-1. During the same period, the growth rate calculated based on one site data is 5.0 nm h-1 using log-normal distribution function method. In light of the fact that considerable uncertainties could be involved in both methods, we consider both estimated growth rates consistent.
- ItemSensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics(Göttingen : Copernicus GmbH, 2009) Kawa, S.R.; Stolarski, R.S.; Newman, P.A.; Douglass, A.R.; Rex, M.; Hofmann, D.J.; Santee, M.L.; Frieler, K.The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate) parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O 2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl 2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS) data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007) are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO + ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen emissions and climate. Further laboratory, theoretical, and possibly atmospheric studies are needed.
- ItemNew particle formation and its effect on cloud condensation nuclei abundance in the summer Arctic: A case study in the Fram Strait and Barents Sea(Katlenburg-Lindau : EGU, 2019) Kecorius, Simonas; Vogl, Teresa; Paasonen, Pauli; Lampilahti, Janne; Rothenberg, Daniel; Wex, Heike; Zeppenfeld, Sebastian; van Pinxteren, Manuela; Hartmann, Markus; Henning, Silvia; Gong, Xianda; Welti, Andre; Kulmala, Markku; Stratmann, Frank; Herrmann, Hartmut; Wiedensohler, AlfredIn a warming Arctic the increased occurrence of new particle formation (NPF) is believed to originate from the declining ice coverage during summertime. Understanding the physico-chemical properties of newly formed particles, as well as mechanisms that control both particle formation and growth in this pristine environment, is important for interpreting aerosol-cloud interactions, to which the Arctic climate can be highly sensitive. In this investigation, we present the analysis of NPF and growth in the high summer Arctic. The measurements were made on-board research vessel Polarstern during the PS106 Arctic expedition. Four distinctive NPF and subsequent particle growth events were observed, during which particle (diameter in a range 10-50 nm) number concentrations increased from background values of approx. 40 up to 4000 cm-3. Based on particle formation and growth rates, as well as hygroscopicity of nucleation and the Aitken mode particles, we distinguished two different types of NPF events. First, some NPF events were favored by negative ions, resulting in more-hygroscopic nucleation mode particles and suggesting sulfuric acid as a precursor gas. Second, other NPF events resulted in less-hygroscopic particles, indicating the influence of organic vapors on particle formation and growth. To test the climatic relevance of NPF and its influence on the cloud condensation nuclei (CCN) budget in the Arctic, we applied a zero-dimensional, adiabatic cloud parcel model. At an updraft velocity of 0.1 m s-1, the particle number size distribution (PNSD) generated during nucleation processes resulted in an increase in the CCN number concentration by a factor of 2 to 5 compared to the background CCN concentrations. This result was confirmed by the directly measured CCN number concentrations. Although particles did not grow beyond 50 nm in diameter and the activated fraction of 15-50 nm particles was on average below 10 %, it could be shown that the sheer number of particles produced by the nucleation process is enough to significantly influence the background CCN number concentration. This implies that NPF can be an important source of CCN in the Arctic. However, more studies should be conducted in the future to understand mechanisms of NPF, sources of precursor gases and condensable vapors, as well as the role of the aged nucleation mode particles in Arctic cloud formation. © Author(s) 2019. This work is distributed under the Creative Commons Attribution 4.0 License.
- ItemCRI-HOM: A novel chemical mechanism for simulating highly oxygenated organic molecules (HOMs) in global chemistry-aerosol-climate models(Katlenburg-Lindau : EGU, 2020) Weber, James; Archer-Nicholls, Scott; Griffiths, Paul; Berndt, Torsten; Jenkin, Michael; Gordon, Hamish; Knote, Christoph; Archibald, Alexander T.We present here results from a new mechanism, CRI-HOM, which we have developed to simulate the formation of highly oxygenated organic molecules (HOMs) from the gas-phase oxidation of-pinene, one of the most widely emitted biogenic volatile organic compounds (BVOCs) by mass. This concise scheme adds 12 species and 66 reactions to the Common Representative Intermediates (CRI) mechanism v2.2 Reduction 5 and enables the representation of semi-explicit HOM treatment suitable for long-term global chemistry-aerosol-climate modelling, within a comprehensive tropospheric chemical mechanism. The key features of the new mechanism are (i) representation of the autoxidation of peroxy radicals from the hydroxyl radical and ozone initiated reactions of-pinene, (ii) formation of multiple generations of peroxy radicals, (iii) formation of accretion products (dimers), and (iv) isoprene-driven suppression of accretion product formation, as observed in experiments. The mechanism has been constructed through optimisation against a series of flow tube laboratory experiments. The mechanism predicts a HOM yield of 2 %-4.5% under conditions of low to moderate NOx , in line with experimental observations, and reproduces qualitatively the decline in HOM yield and concentration at higher NOx levels. The mechanism gives a HOM yield that also increases with temperature, in line with observations, and our mechanism compares favourably to some of the limited observations of [HOM] observed in the boreal forest in Finland and in the southeast USA. The reproduction of isoprene-driven suppression of HOMs is a key step forward as it enables global climate models to capture the interaction between the major BVOC species, along with the potential climatic feedbacks. This suppression is demonstrated when the mechanism is used to simulate atmospheric profiles over the boreal forest and rainforest; different isoprene concentrations result in different [HOM] distributions, illustrating the importance of BVOC interactions in atmospheric composition and climate. Finally particle nucleation rates calculated from [HOM] in present-day and preindustrial atmospheres suggest that "sulfuric-acid-free"nucleation can compete effectively with other nucleation pathways in the boreal forest, particularly in the pre-industrial period, with important implications for the aerosol budget and radiative forcing. © Author(s) 2020.
- ItemInfluence of aerosol copper on HO2 uptake: A novel parameterized equation(Katlenburg-Lindau : EGU, 2020) Song, Huan; Chen, Xiaorui; Lu, Keding; Zou, Qi; Tan, Zhaofeng; Fuchs, Hendrik; Wiedensohler, Alfred; Moon, Daniel R.; Heard, Dwayne E.; Baeza-Romero, MarÃa-Teresa; Zheng, Mei; Wahner, Andreas; Kiendler-Scharr, Astrid; Zhang, YuanhangHeterogeneous uptake of hydroperoxyl radicals (HO2) onto aerosols has been proposed to be a significant sink of HOx , hence impacting the atmospheric oxidation capacity. Accurate calculation of the HO2 uptake coefficient HO2 is key to quantifying the potential impact of this atmospheric process. Laboratory studies show that HO2 can vary by orders of magnitude due to changes in aerosol properties, especially aerosol soluble copper (Cu) concentration and aerosol liquid water content (ALWC). In this study we present a state-of-the-art model called MARK to simulate both gas- and aerosol-phase chemistry for the uptake of HO2 onto Cu-doped aerosols. Moreover, a novel parameterization of HO2 uptake was developed that considers changes in relative humidity (RH) and condensed-phase Cu ion concentrations and which is based on a model optimization using previously published and new laboratory data included in this work. This new parameterization will be applicable to wet aerosols, and it will complement current IUPAC recommendations. The new parameterization is as follows (the explanations for symbols are in the Appendix): (Formula presented) All parameters used in the paper are summarized in Table A1. Using this new equation, field data from a field campaign were used to evaluate the impact of the HO2 uptake onto aerosols on the ROx (=OH+HO2 CRO2) budget. Highly variable values for HO2 uptake were obtained for the North China Plain (median value <0.1). © 2020 Copernicus GmbH. All rights reserved.
- ItemHigh-molecular-weight esters in α-pinene ozonolysis secondary organic aerosol: Structural characterization and mechanistic proposal for their formation from highly oxygenated molecules(Katlenburg-Lindau : EGU, 2018) Kahnt, Ariane; Vermeylen, Reinhilde; Iinuma, Yoshiteru; Safi Shalamzari, Mohammad; Maenhaut, Willy; Claeys, MagdaStable high-molecular-weight esters are present in α-pinene ozonolysis secondary organic aerosol (SOA) with the two most abundant ones corresponding to a hydroxypinonyl ester of cis-pinic acid with a molecular weight (MW) of 368 (C19H28O7) and a diaterpenylic ester of cis-pinic acid with a MW of 358 (C17H26O8). However, their molecular structures are not completely elucidated and their relationship with highly oxygenated molecules (HOMs) in the gas phase is still unclear. In this study, liquid chromatography in combination with positive ion electrospray ionization mass spectrometry has been performed on high-molecular-weight esters present in α-pinene ozonolysis SOA with and without derivatization into methyl esters. Unambiguous evidence could be obtained for the molecular structure of the MWg368 ester in that it corresponds to an ester of cis-pinic acid where the carboxyl substituent of the dimethylcyclobutane ring and not the methylcarboxyl substituent is esterified with 7-hydroxypinonic acid. The same linkage was already proposed in previous work for the MWg358 ester (Yasmeen et al., 2010), but could be supported in the present study. Guided by the molecular structures of these stable esters, we propose a formation mechanism from gas-phase HOMs that takes into account the formation of an unstable C19H28O11 product, which is detected as a major species in α-pinene ozonolysis experiments as well as in the pristine forest atmosphere by chemical ionization-atmospheric pressure ionization-time-of-flight mass spectrometry with nitrate clustering (Ehn et al., 2012, 2014). It is suggested that an acyl peroxy radical related to cis-pinic acid (RO2•) and an alkoxy radical related to 7- or 5-hydroxypinonic acid (R′O•) serve as key gas-phase radicals and combine according to a RO2g+gR′O•→ gRO3R′ radical termination reaction. Subsequently, the unstable C19H28O11 HOM species decompose through the loss of oxygen or ketene from the inner part containing a labile trioxide function and the conversion of the unstable acyl hydroperoxide groups to carboxyl groups, resulting in stable esters with a molecular composition of C19H28O7 (MWg368) and C17H26O8 (MWg358), respectively. The proposed mechanism is supported by several observations reported in the literature. On the basis of the indirect evidence presented in this study, we hypothesize that RO2g+gR′O•→ gRO3R′ chemistry is at the underlying molecular basis of high-molecular-weight ester formation upon α-pinene ozonolysis and may thus be of importance for new particle formation and growth in pristine forested environments.
- ItemLong-term wintertime trend of zonally asymmetric ozone in boreal extratropics during 1979-2016(Basel : MDPI AG, 2018) Schneidereit, A.; Peters, D.H.W.Strong zonally asymmetric ozone (ZAO) changes are observed in the boreal extratropics for winter. During the TOMS (Total Ozone Mapping Spectrometer) period (1979-1992) the decrease of zonally asymmetric total ozone (ZATO) was twice as large as the observed zonal mean total ozone trend over Europe in January mainly caused by ultra-long wave transport. Recent studies have demonstrated that the ozone evolution reveals three different quasi-bidecadal trend stages: (i) Decline, (ii) leveling, and (ii) healing. This study focuses on the ZAO structure in boreal extratropics and on ozone transport changes by ultra-long waves during winter months. ERA-Interim data together with a linearized transport model are used. During the healing stage ZATO increases significantly over the North Atlantic/European region for January. The ZATO increase (healing stage) and ZATO decrease (decline stage) are caused by different monthly mean ozone transport characteristics of ultra-long planetary waves over the North Atlantic/European region. Furthermore, the vertical advection (ageostrophic transport) of ozone versus its horizontal component dominates in the lower and middle stratosphere during the healing stage. It is hypothesized that these ageostrophic wind changes are mainly caused by a wave train directed northeastwards which seems to be directly linked to the Arctic warming. © 2018 by the authors.
- ItemNOy production, ozone loss and changes in net radiative heating due to energetic particle precipitation in 2002–2010(Katlenburg-Lindau : EGU, 2018-1-29) Sinnhuber, Miriam; Berger, Uwe; Funke, Bernd; Nieder, Holger; Reddmann, Thomas; Stiller, Gabriele; Versick, Stefan; von Clarmann, Thomas; Wissing, Jan MaikWe analyze the impact of energetic particle precipitation on the stratospheric nitrogen budget, ozone abundances and net radiative heating using results from three global chemistry-climate models considering solar protons and geomagnetic forcing due to auroral or radiation belt electrons. Two of the models cover the atmosphere up to the lower thermosphere, the source region of auroral NO production. Geomagnetic forcing in these models is included by prescribed ionization rates. One model reaches up to about 80 km, and geomagnetic forcing is included by applying an upper boundary condition of auroral NO mixing ratios parameterized as a function of geomagnetic activity. Despite the differences in the implementation of the particle effect, the resulting modeled NOy in the upper mesosphere agrees well between all three models, demonstrating that geomagnetic forcing is represented in a consistent way either by prescribing ionization rates or by prescribing NOy at the model top. Compared with observations of stratospheric and mesospheric NOy from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument for the years 2002–2010, the model simulations reproduce the spatial pattern and temporal evolution well. However, after strong sudden stratospheric warmings, particle-induced NOy is underestimated by both high-top models, and after the solar proton event in October 2003, NOy is overestimated by all three models. Model results indicate that the large solar proton event in October 2003 contributed about 1–2 Gmol (109 mol) NOy per hemisphere to the stratospheric NOy budget, while downwelling of auroral NOx from the upper mesosphere and lower thermosphere contributes up to 4 Gmol NOy. Accumulation over time leads to a constant particle-induced background of about 0.5–1 Gmol per hemisphere during solar minimum, and up to 2 Gmol per hemisphere during solar maximum. Related negative anomalies of ozone are predicted by the models in nearly every polar winter, ranging from 10–50 % during solar maximum to 2–10 % during solar minimum. Ozone loss continues throughout polar summer after strong solar proton events in the Southern Hemisphere and after large sudden stratospheric warmings in the Northern Hemisphere. During mid-winter, the ozone loss causes a reduction of the infrared radiative cooling, i.e., a positive change of the net radiative heating (effective warming), in agreement with analyses of geomagnetic forcing in stratospheric temperatures which show a warming in the late winter upper stratosphere. In late winter and spring, the sign of the net radiative heating change turns to negative (effective cooling). This spring-time cooling lasts well into summer and continues until the following autumn after large solar proton events in the Southern Hemisphere, and after sudden stratospheric warmings in the Northern Hemisphere.