ALBERT

Description: Black carbon reduction will weaken the aerosol net cooling effect Atmospheric Chemistry and Physics Discussions, 14, 33117-33141, 2014 Author(s): Z. L. Wang, H. Zhang, and X. Y. Zhang Black carbon (BC), a distinct type of carbonaceous material formed from the incomplete combustion of fossil and biomass based fuels under certain conditions, can interact with solar radiation and clouds through its strong light-absorption ability, thereby warming the Earth's climate system. Some studies have even suggested that global warming could be slowed down in a short term by eliminating BC emission due to its short lifetime. In this study, we estimate the influence of removing some sources of BC and other co-emitted species on the aerosol radiative effect by using an aerosol-climate coupled model BCC_AGCM2.0.1_CUACE/Aero, in combination with the aerosol emissions from the Representative Concentration Pathways (RCPs) scenarios. We find that the global annual mean aerosol net cooling effect at the top of the atmosphere (TOA) will be enhanced by 0.12 W m −2 compared with present-day conditions if the BC emission is reduced exclusively to the level projected for 2100 based on the RCP2.6 scenario. This will be beneficial for the mitigation of global warming. However, the global annual mean aerosol net cooling effect at the TOA will be weakened by 1.7–2.0 W m −2 relative to present-day conditions if emissions of BC and co-emitted sulfur dioxide and organic carbon are simultaneously reduced as the most close conditions to the actual situation to the level projected for 2100 in different ways based on the RCP2.6, RCP4.5, and RCP8.5 scenarios. Because there are no effective ways to remove the BC exclusively without influencing the other co-emitted components, our results therefore indicate that a reduction in BC emission can lead to an unexpected warming on the Earth's climate system in the future.

Description: Characterization of the boundary layer at Dome C (East Antarctica) during the OPALE summer campaign Atmospheric Chemistry and Physics Discussions, 14, 33089-33116, 2014 Author(s): H. Gallée, S. Preunkert, S. Argentini, M. M. Frey, C. Genthon, B. Jourdain, I. Pietroni, G. Casasanta, H. Barral, E. Vignon, and M. Legrand The regional climate model MAR was run for the region of Dome C located on the East Antarctic plateau, during Antarctic summer 2011–2012, in order to refine our understanding of meteorological conditions during the OPALE observation campaign. A very high vertical resolution is set up in the lower troposphere, with a grid spacing of roughly 2 m. Comparisons are made with observed temperatures and winds near the surface and from a 45 m high tower as well as sodar and radiation data. MAR is generally in very good agreement with the observations but sometimes underestimates cloud formation, leading to an underestimation of the simulated downward long-wave radiation. Absorbed short-wave radiation may also be slightly overestimated due to an underestimation of the snow albedo and this influences the surface energy budget and atmospheric turbulence. Nevertheless the model provides sufficiently reliable information that represent key parameters when discussing the representativeness of chemical measurements made nearby the ground surface during field campaigns conducted at the Concordia site located at Dome C (3233 m a.s.l.).

Description: Isotopic effects of nitrate photochemistry in snow: a field study at Dome C, Antarctica Atmospheric Chemistry and Physics Discussions, 14, 33045-33088, 2014 Author(s): T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson Stable isotope ratios of nitrate preserved in deep ice cores are expected to provide unique and valuable information regarding paleo-atmospheric processes. However, due to the post-depositional loss of nitrate in snow, this information may be erased or significantly modified by physical or photochemical processes before preservation in ice. We have investigated the role of solar UV photolysis in the post-depositional modification of nitrate mass and stable isotope ratios at Dome C, Antarctica during the austral summer of 2011/12. Two 30 cm snow pits were filled with homogenized drifted snow from the vicinity of the base. One of these pits was covered with a plexiglass plate that transmits solar UV radiation, while the other was covered with a different plexiglass plate having a low UV transmittance. Samples were then collected from each pit at a 2–5 cm depth resolution and a 10 day frequency. At the end of the season, a comparable nitrate mass loss was observed in both pits for the top-level samples (0–7 cm). At deeper levels (7–30 cm), a significant nitrate mass loss (ca. 30%) was observed in the UV-exposed pit relative to the control field. From the nitrate stable isotope ratios and concentration losses measured in the snow nitrate exposed to solar UV, we have derived average apparent isotopic fractionations ( 15 ϵ, 18 ϵ and 17 E) of −67.8 ± 12‰, 12.5 ± 6.7‰ and 2.2 ± 1.4‰ for δ 15 N, δ 18 O, and Δ 17 O, respectively. These values are fairly stable throughout the season and are in close agreement with the apparent fractionations measured in natural snow at Dome C. Meanwhile, for the control samples in which solar UV was blocked, an apparent average 15 ϵ value of −12.0 ± 1.7‰ was derived. The difference in the apparent 15 ϵ values obtained for the two experimental fields strongly suggests that solar UV photolysis plays a dominant role in driving observed nitrate mass loss and resulting isotopic fractionation. We have also observed an insensitivity of 15 ϵ with depth in the snowpack under the given experimental setup. This is due to the uniform attenuation of incoming solar UV by snow, as 15 ϵ is strongly dependent on the shape of the incoming light flux. Together with earlier work, the results presented here represent a strong body of evidence that solar UV photolysis is the most relevant post-depositional process modifying the mass and stable isotope ratios of snow nitrate at low accumulation sites where most deep ice cores are drilled. Nevertheless, modeling the loss of nitrate in snow is still required before a robust interpretation of ice core records can be provided.

Description: OH populations and temperatures from simultaneous spectroscopic observations of 25 bands Atmospheric Chemistry and Physics Discussions, 14, 32979-33043, 2014 Author(s): S. Noll, W. Kausch, S. Kimeswenger, S. Unterguggenberger, and A. M. Jones OH rotational temperatures are widely used to derive mesopause temperatures and their variations. Since most data sets are only based on a fixed set of lines of a single band, it is important to know possible systematic uncertainties related to the choice of lines. Therefore, a comprehensive study of as many as possible OH bands is desirable. For this purpose, astronomical echelle spectrographs at large telescopes are the most suitable instruments. They offer a wide wavelength coverage, relatively high spectral resolution, and high sensitivity. Moreover, since each ground-based astronomical observation has an imprint of the Earth's atmosphere, the data archives of large astronomical facilities are a treasure for atmospheric studies. For our project, we used archival data of the medium-resolution X-shooter echelle spectrograph operated by the European Southern Observatory at Cerro Paranal in Chile. The instrument can simultaneously observe all OH bands that are accessible from ground. We reduced and analysed a set of 343 high-quality spectra taken between 2009 and 2013 to measure OH line intensities and to derive rotational and vibrational temperatures of 25 bands from OH(8-2) to OH(9-7). We studied the influence of the selected line set, OH band, upper vibrational level v ′ , and the molecular data on the derived level populations and temperatures. The rotational temperature results indicate differences by several degrees depending on the selection. There is a discrepancy for bands of even and odd v ′ , which increases with v ′ . A study of the temporal variations revealed that the v ′ from to 2 to 9 show a clear trend in the change of the variability pattern. In particular, the spread of temperatures tends to increase during the night, and the time of the minimum temperature depends on v ′ . The vibrational temperatures depend on the range of v ′ used for their determination, since the higher vibrational levels from 7 to 9 seem to be overpopulated compared to the lower levels. The vibrational temperature tends to increase during the night, while the intensity decreases. Our results support the assumption that the OH emission altitude depends on v ′ . Moreover, the emission layer appears to rise in the course of the night, which makes the OH thermalisation less efficient. The derived rotational temperatures and their change with v ′ seem to be significantly affected by non-equilibrium populations.

Description: Hygroscopic properties of NaCl and NaNO 3 mixture particles as reacted inorganic sea-salt aerosol surrogates Atmospheric Chemistry and Physics Discussions, 14, 33143-33183, 2014 Author(s): D. Gupta, H. Kim, G. Park, X. Li, H.-J. Eom, and C.-U. Ro NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NO x / HNO 3 , so internally mixed NaCl and NaNO 3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO 3 mixture particles at ten mixing ratios (mole fractions of NaCl ( X NaCl ) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition ( X NaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9(± 0.5)%. On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions, i.e., the eutonic component dissolved at MDRH and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles ( X NaCl 〉 0.38) showed two-stage efflorescence transitions: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0–35.5%. Interestingly, aerosol particles with the eutonic composition ( X NaCl = 0.38) also showed two-stage efflorescence with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO 3 on the NaCl seeds. NaNO 3 -rich particles X NaCl ≤ 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH, because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO 3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl-NaNO 3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for X NaCl 〉 0.38) or NaNO 3 (for X NaCl ≤ 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of remnant pure salts (NaCl or NaNO 3 in NaCl- or NaNO 3 -rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl-NaNO 3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than the genuine SSA surrogate (i.e., pure NaCl particles), making their heterogeneous chemistry more probable.

Description: Influence of particle phase state on the hygroscopic behavior of mixed organic–inorganic aerosols Atmospheric Chemistry and Physics Discussions, 14, 32935-32977, 2014 Author(s): N. Hodas, A. Zuend, W. Mui, R. C. Flagan, and J. H. Seinfeld Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids, to phase-separated particles, to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40–90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids, (2) forcing a single phase, but accounting for non-ideal interactions through activity coefficient calculations, and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation between the inorganic and organic components is assumed at all RH values, with water-uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that a single simplified modeling approach cannot be used to capture the water-uptake behavior for the diversity of particle phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to contribute substantially to error in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.

Description: The diurnal variation in stratospheric ozone from the MACC reanalysis, the ERA-Interim reanalysis, WACCM and Earth observation data: characteristics and intercomparison Atmospheric Chemistry and Physics Discussions, 14, 32667-32708, 2014 Author(s): A. Schanz, K. Hocke, N. Kämpfer, S. Chabrillat, A. Inness, M. Palm, J. Notholt, I. Boyd, A. Parrish, and Y. Kasai In this study we compare the diurnal variation in stratospheric ozone derived from free-running simulations of the Whole Atmosphere Community Climate Model (WACCM) and from reanalysis data of the atmospheric service MACC (Monitoring Atmospheric Composition and Climate) which both use a similar stratospheric chemistry module. We find good agreement between WACCM and the MACC reanalysis for the diurnal ozone variation in the high-latitude summer stratosphere based on photochemistry. In addition, we consult the ozone data product of the ERA-Interim reanalysis. The ERA-Interim reanalysis ozone system with its long-term ozone parametrization can not capture these diurnal variations in the upper stratosphere that are due to photochemistry. The good dynamics representations, however, reflects well dynamically induced ozone variations in the lower stratosphere. For the high-latitude winter stratosphere we describe a novel feature of diurnal variation in ozone where changes of up to 46.6% (3.3 ppmv) occur in monthly mean data. For this effect good agreement between the ERA-Interim reanalysis and the MACC reanalysis suggest quite similar diurnal advection processes of ozone. The free-running WACCM model seriously underestimates the role of diurnal advection processes at the polar vortex at the two tested resolutions. The intercomparison of the MACC reanalysis and the ERA-Interim reanalysis demonstrates how global reanalyses can benefit from a chemical representation held by a chemical transport model. The MACC reanalysis provides an unprecedented description of the dynamics and photochemistry of the diurnal variation of stratospheric ozone which is of high interest for ozone trend analysis and research on atmospheric tides. We confirm the diurnal variation in ozone at 5 hPa by observations of the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) experiment and selected sites of the Network for Detection of Atmospheric Composition Change (NDACC). The latter give valuable insight even to diurnal variation of ozone in the polar winter stratosphere.

Description: Ash iron mobilization in volcanic eruption plumes Atmospheric Chemistry and Physics Discussions, 14, 32535-32581, 2014 Author(s): G. Hoshyaripour, M. Hort, and B. Langmann It has been shown that volcanic ash fertilizes the Fe-limited areas of the surface ocean through releasing soluble iron. As ash iron is mostly insoluble upon the eruption, it is hypothesized that heterogeneous in-plume and in-cloud processing of the ash promote the iron solubilization. Direct evidences concerning such processes are, however, lacking. In this study, a 1-D numerical model is developed to simulate the physicochemical interactions of gas–ash–aerosol in volcanic eruption plumes focusing on the iron mobilization processes at temperatures between 600 and 0 °C. Results show that sulfuric acid and water vapor condense at ~150 and ~50 °C on the ash surface, respectively. This liquid phase then efficiently scavenges the surrounding gases (〉95% of HCl, 3–20% of SO 2 and 12–62% of HF) forming an extremely acidic coating at the ash surface. The low pH conditions of the aqueous film promote acid-mediated dissolution of the Fe-bearing phases present in the ash material. We estimate that 0.1 to 33% of the total iron available at the ash surface is dissolved in the aqueous phase before the freezing point is reached. The efficiency of dissolution is controlled by the halogen content of the erupted gas as well as the mineralogy of the iron at ash surface: elevated halogen concentrations and presence of Fe 2+ -carrying phases lead to the highest dissolution efficiency. Findings of this study are in agreement with the data obtained through leaching experiments.

Description: Tropospheric ozone and its precursors from the urban to the global scale from air quality to short-lived climate forcer Atmospheric Chemistry and Physics Discussions, 14, 32709-32933, 2014 Author(s): P. S. Monks, A. T. Archibald, A. Colette, O. Cooper, M. Coyle, R. Derwent, D. Fowler, C. Granier, K. S. Law, D. S. Stevenson, O. Tarasova, V. Thouret, E. von Schneidemesser, R. Sommariva, O. Wild, and M. L. Williams Ozone holds a certain fascination in atmospheric science. It is ubiquitous in the atmosphere, central to tropospheric oxidation chemistry, yet harmful to human and ecosystem health as well as being an important greenhouse gas. It is not emitted into the atmosphere but is a by-product of the very oxidation chemistry it largely initiates. Much effort is focussed on the reduction of surface levels of ozone owing to its health impacts but recent efforts to achieve reductions in exposure at a country scale have proved difficult to achieve due to increases in background ozone at the zonal hemispheric scale. There is also a growing realisation that the role of ozone as a short-lived climate pollutant could be important in integrated air quality climate-change mitigation. This review examines current understanding of the processes regulating tropospheric ozone at global to local scales from both measurements and models. It takes the view that knowledge across the scales is important for dealing with air quality and climate change in a synergistic manner.

Description: Origin of springtime ozone enhancements in the lower troposphere over Beijing: in situ measurements and model analysis Atmospheric Chemistry and Physics Discussions, 14, 32583-32627, 2014 Author(s): J. Huang, H. Liu, J. H. Crawford, C. Chan, D. B. Considine, Y. Zhang, X. Zheng, C. Zhao, V. Thouret, S. J. Oltmans, S. C. Liu, D. B. A. Jones, S. D. Steenrod, and M. R. Damon Ozone (O 3 ) concentrations in the lower troposphere (LT) over Beijing have significantly increased over the past two decades as a result of rapid industrialization in China, with important implications for regional air quality and photochemistry of the background troposphere. We characterize the vertical distribution of lower-tropospheric (0–6 km) O 3 over Beijing using observations from 16 ozonesonde soundings made during a field campaign in April–May 2005 and MOZAIC (Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft) aircraft measurements over 13 days in the same period. We focus on the origin of LT O 3 enhancements observed over Beijing, particularly in May. We use a global 3-D chemistry and transport model (GEOS-Chem CTM) driven by assimilated meteorological fields to examine the transport pathways for O 3 pollution, and quantify the sources contributing to O 3 and its enhancements in the springtime LT over Beijing. Output from the Global Modeling Initiative (GMI) CTM is also used. High O 3 concentrations (up to 94.7 ppbv) were frequently observed at the altitude of ~1.5–2 km. The CTMs captured the timing of the occurrences but significantly underestimated their magnitude. GEOS-Chem simulations and a case study showed that O 3 produced in the Asian troposphere (especially from Asian anthropogenic pollution) made major contributions to the observed O 3 enhancements. Contributions from anthropogenic pollution in the European and North American troposphere were reduced during these events, in contrast with days without O 3 enhancements, when contributions from Europe and North America were substantial. The O 3 enhancements typically occurred under southerly wind and warmer conditions. It is suggested that an earlier onset of the Asian summer monsoon would cause more O 3 enhancement events in the lower troposphere over the North China Plain in late spring and early summer.